- Phosphine-Catalyzed Cascade Annulation of MBH Carbonates and Diazenes: Synthesis of Hexahydrocyclopenta[c]pyrazole Derivatives
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A phosphine-catalyzed cascade annulation of Morita-Baylis-Hillman (MBH) carbonates and diazenes was achieved, giving tetrahydropyrazole-fused heterocycles bearing two five-membered rings in moderate to excellent yields. The reaction underwent an unprecedented reaction mode of MBH carbonates, in which two molecules of MBH carbonates were fully merged into the ring system.
- Guo, Hongchao,Li, Hongxiang,Liu, Hao,Shi, Wangyu,Wang, Chang,Wang, Wei,Wu, Yongjun
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supporting information
p. 5571 - 5575
(2021/07/31)
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- A Method For Preparing (Meth)Acrylic Acid Ester Based Compound
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The invention relates to a method for preparing a (meth)acrylic acid ester-based compound, and according to the preparation method, a (meth)acrylic acid ester-based compound can be prepared with high purity and high yield, by easily introducing an acrylic structure into alcohol using a diamine-based compound and acid anhydride.
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Paragraph 0073
(2021/05/07)
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- Activated Self-Resolution and Error-Correction in Catalytic Reaction Networks**
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Understanding the emergence of function in complex reaction networks is a primary goal of systems chemistry and origin-of-life studies. Especially challenging is to create systems that simultaneously exhibit several emergent functions that can be independently tuned. In this work, a multifunctional complex reaction network of nucleophilic small molecule catalysts for the Morita-Baylis-Hillman (MBH) reaction is demonstrated. The dynamic system exhibited triggered self-resolution, preferentially amplifying a specific catalyst/product set out of a many potential alternatives. By utilizing selective reversibility of the products of the reaction set, systemic thermodynamically driven error-correction could also be introduced. To achieve this, a dynamic covalent MBH reaction based on adducts with internal H-transfer capabilities was developed. By careful tuning of the substituents, rate accelerations of retro-MBH reactions of up to four orders of magnitude could be obtained. This study thus demonstrates how efficient self-sorting of catalytic systems can be achieved through an interplay of several complex emergent functionalities.
- Schaufelberger, Fredrik,Ramstr?m, Olof
-
supporting information
p. 10335 - 10340
(2021/05/07)
-
- Palladium-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted: O-carboranes containing α,β-unsaturated carbonyls
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With the help of a carboxylic acid directing group, Pd-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted o-carboranes containing α,β-unsaturated carbonyls has been reported. The-COOH, removed during the course of the reaction, is responsible for controlling the regioselectivity. The desired products could be obtained in moderate to good yields.
- Li, Jiaoyi,Lu, Jian,Tian, Song,Wang, Qian,Zhang, Chuyi,Zhang, Jianwei,Zhou, Ling
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p. 4723 - 4727
(2020/07/13)
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- Ruthenium(II) Catalysed Highly Regioselective C-3 Alkenylation of Indolizines and Pyrrolo[1,2-a]quinolines
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Discovered the Ruthenium(II) catalysed highly stereo- and regioselective protocol for the oxidative C-3 alkenylation of indolizines and pyrrolo[1,2-a]quinolines. The methodology represents the first example for the directing group assisted C–C bond formation reaction of the indolizines. Under mild reaction conditions, this method provides an ample substrate scope to produce C-3 alkenyl indolizines in excellent to moderate yields. However, pyrrolo[1,2-a]quinolines underwent alkenynation at elevated temperature to furnish C-3 alkenyl derivatives. The functionalized indolizines were selectively reduced to obtain their saturated derivatives.
- Jadhav, Pankaj Pandit,Kahar, Nilesh Machhindra,Dawande, Sudam Ganpat
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supporting information
p. 7831 - 7835
(2019/12/24)
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- Ruthenium(II) oxidase catalysis for C-H alkenylations in biomass-derived γ-valerolactone
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Ruthenium(ii) biscarboxylate oxidase catalysis is a powerful tool for the assembly of functionalized arenes with oxygen as a green oxidant, but this strategy was thus far limited to its use in traditional organic solvents. Herein, we report on a green procedure for the ruthenium(ii) biscarboxylate-catalysed C-H functionalisation in biomass-derived γ-valerolactone as the reaction medium. The oxidase catalysis was characterized by ample substrate scope and proceeded efficiently with oxygen as the sole oxidant. The overall green nature of this C-H-activation methodology is reflected by H2O being the only by-product.
- Bechtoldt, Alexander,Baumert, Marcel E.,Vaccaro, Luigi,Ackermann, Lutz
-
supporting information
p. 398 - 402
(2018/02/07)
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- CATALYTIC ESTER DECARBONYLATION
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A process of preparing olefins of the formula (I) is described herein: with R1 being a substituted or unsubstituted (C1-C30)hydrocarbyl, and R2 being a substituted or unsubstituted (C1-C20)hydrocarbyl. The process includes reacting a compound of formula (II) wherein Ar is chosen from in the presence of a palladium-based catalyst and an organic solvent. A process of preparing olefins of the formula (III) is also described: with R3 being a substituted or unsubstituted (C1-C30)hydrocarbyl, R4 being a substituted or unsubstituted (C1-C20)hydrocarbyl, and R5 being a substituted or unsubstituted (C1-C30) hydrocarbyl. The process includes reacting a compound of formula (IV) wherein Ar is chosen from with a compound of formula (V) wherein Ar is chosen from in the presence of a palladium-based catalyst and an organic solvent.
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-
Paragraph 0071-0072: 0074
(2016/08/07)
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- Trimaleimide Linkers and Uses Thereof
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A type of trimaleimide linkers and uses thereof are disclosed. The trimaleimide linkers can be applied for preparation of antibody-drug conjugate as shown by formula I: L– (T–A–D) n Ⅰ wherein, L is an antibody, antibody fragment or protein; T is a trimaleimide linker; A is a cleavable linker group or a noncleavable linker; D is a drug; n is an integer ranging from 1 to 8.
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Page/Page column 28
(2016/12/22)
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- In a strongly acidic cation exchange resin as catalyst catalytic synthesis process for the preparation of acrylic acid T-butyl ester
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The invention discloses a preparation process for catalyzing and synthesizing tert-butyl acrylate by using strong acid cation exchange resin as a catalyst, belonging to the technical field of organic synthesis. The preparation process is characterized by comprising the steps of: adding crylic acid, strong acid cation exchange resin, a polymerization inhibitor A and a polymerization inhibitor B into a closed reaction kettle, dropwise adding liquefied isobutene for carrying out esterification reaction; after dropwise adding is completed, carrying out thermal insulation; after the thermal insulation is finished, releasing the pressure of the closed reaction kettle, filtering, extracting a liquid component to enter a rectifying tower; and sequentially separating byproducts of tertiary butanol and diisobutylene and a target project of the tert-butyl acrylate. The preparation process has the beneficial effects that the liquefied isobutene is adopted to be directly catalyzed together with the crylic acid and the cation exchange resin under the action of the polymerization inhibitor A and the polymerization inhibitor B to form a specific catalysis system, gaseous isobutene is not needed to be dissolved in a solvent containing crylic acid for carrying out esterification reaction under the action of the catalyst, and thus the procedure of absorbing a solvent in subsequent operation is removed, resources are saved and procedures are saved.
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-
Paragraph 0031; 0036-0041
(2017/02/02)
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- Double-modified mesoporous molecular sieve catalytic SBA method for preparing carboxylic acid T-butyl ester
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The invention discloses a method for preparing tert-butyl carboxylate by using a dual-modified SBA mesoporous molecular sieve catalyst. According to the method, carboxylic acid and isobutylene are subjected to addition esterification by using a dual-modified SBA mesoporous molecular sieve as a catalyst to synthesize the tert-butyl carboxylate. The molecular sieve catalyst is a metal-doped sulfonate-grafted dual-modified SBA mesoporous molecular sieve catalyst prepared by a one-step cocondensation process. When the dual-modified SBA mesoporous molecular sieve catalyst is used in the addition esterification reaction process of synthesizing tert-butyl carboxylic acid from carboxylic acid and isobutylene, no polar solvent (such as tert-butyl alcohol, methyl tert-butyl ether or the like) is needed as an isobutylene polymerization inhibitor, and the quantity of the carboxylic acid is not excessive, thereby reducing the energy consumption for separating the reaction product. The catalyst has the advantages of high conversion rate, high selectivity, non-homogeneous phase, no corrosiveness, adjustable acid quantity and acid center and the like, and is recyclable.
- -
-
Paragraph 0042; 0043
(2016/11/21)
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- Olefins from biomass feedstocks: Catalytic ester decarbonylation and tandem Heck-type coupling
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With the goal of avoiding the need for anhydride additives, the catalytic decarbonylation of p-nitrophenylesters of aliphatic carboxylic acids to their corresponding olefins, including commodity monomers like styrene and acrylates, has been developed. The reaction is catalyzed by palladium complexes in the absence of added ligands and is promoted by alkali/alkaline-earth metal halides. Combination of catalytic decarbonylation and Heck-type coupling with aryl esters in a single pot process demonstrates the viability of employing a carboxylic acid as a "masked olefin" in synthetic processes. This journal is
- John, Alex,Hogan, Levi T.,Hillmyer, Marc A.,Tolman, William B.
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supporting information
p. 2731 - 2733
(2015/03/05)
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- Catalytic decarbonylation of biomass-derived carboxylic acids as efficient route to commodity monomers
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The palladium-catalyzed decarbonylation of bio-derived carboxylic acids to alkyl acrylates, styrene, and acrylonitrile is reported. The olefins were isolated by continuous distillation in yields up to 87% by heating a neat, equimolar mixture of pivalic anhydride with the appropriate carboxylic acid to 190 °C in the presence of a Pd-phosphine catalyst.
- Miranda, Maria O.,Pietrangelo, Agostino,Hillmyer, Marc A.,Tolman, William B.
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experimental part
p. 490 - 494
(2012/04/10)
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- BLOCK POLYMER, COSMETIC COMPOSITION COMPRISING IT AND COSMETIC TREATMENT PROCESS
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A block polymer containing, in a block with a Tg greater than 20° C., at least one monomer of formula (I): The invention also relates to a cosmetic composition comprising the block polymer in a cosmetically acceptable medium, and also to a cosmetic process for treating keratin materials using the composition, and most particularly to a process for making up the lips.
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- BLOCK POLYMER, COSMETIC COMPOSITION COMPRISING IT AND COSMETIC TREATMENT PROCESS
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A block polymer containing, in a block with a Tg of less than 20° C., at least one monomer of formula (I): The invention also relates to a cosmetic composition containing the block polymer in a cosmetically acceptable medium, and also to a cosmetic process for treating keratin materials using the composition, and most particularly to a process for making up the lips.
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- PROCESS FOR PREPARING TERTIARY ALKYL ESTERS OF (METH) ACRYLIC ACID HAVING AT LEAST 4 CARBON ATOMS IN THE ALKYL RADICAL
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A process for preparing tertiary alkyl esters of (meth)acrylic acid having at least 4 carbon atoms in the alkyl radical, comprising the steps of: (1) reacting (meth)acrylic acid with at least one olefin of the general formula I: in which R1 and R2 are an alkyl radical, and R3 is a hydrogen atom, an alkyl radical, a cycloalkyl radical, an aryl radical, an alkylcycloalkyl radical, an alkylaryl radical, a cycloalkylaryl radical, or an alkylcycloalkylaryl radical; in homogeneous phase in the presence of an acidic catalyst in a reactor, (2) discharging the resulting reaction mixture (1) from the reactor, (3) separating the discharged reaction mixture (2) into a mixture (3.1) which comprises the catalyst and a mixture (3.2) which comprises the tertiary alkyl ester of (meth)acrylic acid having at least 4 carbon atoms in the alkyl radical, and (4) removing the tertiary alkyl ester of (meth)acrylic acid having at least 4 carbon atoms in the alkyl radical from the mixture (3.2), wherein, (5) in process step (4), at least one compound S which comprises at least one N-oxyl group is added as a stabilizer.
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Page/Page column 5
(2009/02/11)
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- Asymmetric Diels-Alder reaction between acrylates and cyclopentadiene in the presence of chiral catalysts
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Asymmetric Diels-Alder reaction between cyclopentadiene and alkyl and cycloalkyl acrylates in the presence of new chiral catalysts, BBr 3?MentOEt, AlCl2OMent, BBr2OMent, and BBr(OMent)2, was studied. Optically active bicyclo[2.2.1]hept-2-ene- 5-carboxylates were synthesized. The influence of the reaction conditions on the total and optical yields and on the stereoselectivity of the adducts synthesized was examined. Nauka/Interperiodica 2006.
- Mamedov
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p. 1621 - 1625
(2008/02/07)
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- MULTI-DENTATE LATE TRANSITION METAL CATALYST COMPLEXES AND POLYMERIZATION METHODS USING THOSE COMPLEXES
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The instant invention provides a late transition metal complex which can be used with an activating cocatalyst to produce polymers and copolymers. The invention also provides methods for polymerizing olefins, as well as copolymers having polar monomers incorporated therein. More specifically, the invention provides a composition having the formula LMXZn, wherein M is selected from the group consisting of Cu, Ag and Au; X is selected from the group consisting of halide, hydride, triflate, acetate, borate, C1 through C12 alkyl, C1 through C12 alkoxy, C3 through C12 cycloalkyl, C3 through C12 cycloalkoxy, aryl, thiolate, nitrate, sulfate, nitrile, hydroxide and any other moiety into which a monomer can insert; Z is selected from the group consisting of halide, hydride, triflate, acetate, borate, C1 through C12 alkyl, C1 through C12 alkoxy, C3 through C12 cycloalkyl, C3 through C12 cycloalkoxy, aryl, thiolate, carbon monoxide, nitrate, nitrile, hydroxide, sulfate, olefins, water, any other neutral coordinating ligand and any other moiety into which a monomer can insert; n equals 0, 1 or 2; and L is a multi-dentate nitrogen-containing ligand.
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- COSMETIC POLYMER COMPOSITION AND COSMETIC
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The present invention discloses a cosmetic polymer composition containing a straight-chain block copolymer, where the copolymer having a unit derived from a compound having an ethylenic unsaturated bond, having a number-average molecular weight of 1.0×103 to 1.0×106, and having at least two or more glass transition points or melting points; a hair cosmetic polymer composition containing a copolymer a copolymer capable of forming a film having a Young's modulus of 50 MPa or larger and a fracture-point elongation of 100% or larger, and dispersible into water and/or alcohol; and a cosmetic material containing these compositions.
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- Method for producing tertiary c4-c8-alkyl esters of (meth)acryl acid
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A tert-C4-C8-alkyl (meth)acrylate is prepared by reacting (meth)acrylic acid with an olefin of the formula where R1 and R2, which may be identical or different, are methyl or ethyl and R3 is H, methyl or ethyl, in homogeneous phase in the presence of an acidic catalyst and isolating the tert-C4-C8-alkyl (meth)acrylate from the reaction mixture, by a process in which the catalyst is separated off as residue by a two-stage distillation of the reaction mixture and the tert-C4-C8-alkyl (meth)acrylate is isolated from the distillates. The novel process makes it possible to use acetic acid-containing (meth)acrylic acid. The danger of cleavage of the ester and of polymerization of (meth)acrylic compounds is reduced.
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- Process for the conversion of aldehydes to esters
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A process for the conversion of aldehydes to esters, specifically acrolein or methacrolein to methyl acrylate or methyl methacrylate, respectively. Essentially in the absence of water, an aldehyde is contacted with an oxidizing agent to form an intermediate and then the intermediate is contacted with a diol or an alcohol to form an ester or diester. Preferably, the oxidizing agent is also a chlorinating agent. Specifically, acrolein or methacrolein is contacted with an oxidizing/chlorinating agent, such as t-butyl hypochlorite, and the chlorinated compound is contacted with an alcohol, such as methanol, to form methyl acrylate or methyl methacrylate, respectively. Generally, the order of addition is for the oxidizing agent to be added to the aldehyde, specifically for t-butyl hypochlorite to be added to acrolein or methacrolein, and for the diol or alcohol to be added to the intermediate, specifically for the methanol to be added to the reaction product of acrolein or methacrolein and t-butyl hypochlorite. The process of the present invention can be carried out in the absence or in the presence of solvent. Generally, better methyl acrylate or methyl methacrylate yields are obtained at lower reaction temperatures.
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Page/Page column 3-4
(2010/01/31)
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- Does the DABCO-catalysed reaction of 2-hydroxybenzaldehydes with methyl acrylate follow a Baylis-Hillman pathway?
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Evidence is presented which supports the intermediacy of dipolar Baylis-Hillman-type adducts in the synthesis of coumarin and chromene derivatives from the reaction of 2-hydroxybenzaldehydes with methyl acrylate in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO).
- Kaye, Perry T.,Musa, Musiliyu A.,Nocanda, Xolani W.,Robinson, Ross S.
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p. 1133 - 1138
(2007/10/03)
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- Preparation of preparing substituted indanones
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a process for the preparation of indanones of the formula II from, indanones of the formula I or of indanones of the formula IIa from indanones of the formula Ia comprises reacting an indanone of the formula I or Ia with a coupling component.
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- Syntheses and reactivities of hydrosulfido- or sulfido-bridged heterobimetallic complexes containing group 6 and group 9 metals
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Reactions of [Cp2M(SH)2] (M = Mo 1, W 2) with one equiv of [IrH2(PPh3)2(Me2CO)2][PF 6] in acetone at room temperature under 1 atm of H2 afforded the hydrosu
- Kato, Hiroko,Seino, Hidetake,Mizobe, Yasushi,Hidai, Masanobu
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p. 1494 - 1499
(2007/10/03)
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- Substituted thiol macrolactam immunomodulators
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Immunomodulatory macrocyclic compounds having the formula: STR1 and pharmaceutically acceptable salts, esters, amides and prodrugs thereof, as well as pharmaceutical compositions containing such compounds and therapeutic methods of their use.
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- Indole derivatives as 5-HT1-like agonists
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Compounds of formula (I) and pharmaceutically acceptable salts thereof, wherein R1 is a substituted alkylene; C3 -C7 cycloalkyl optionally substituted with HO; C3 -C6 alkenyl optionally substituted with aryl; C5 -C7 cycloalkenyl; or C3 -C6 alkynyl; R2 is H; halo; F3 C; NC; R8 R9 NOC; a substituted alkylene; R8 R9 NO2 S; R10 S(O)m ; R12 CON(R11); R10 SO2 N(R11); R8 R9 NOCN(R11); R10 O2 CN(R11); R13 (CH2)n CH=CH; or R7 O are selective 5-HT1 -like receptor agonists useful in the treatment of migraine, cluster headache, chronic paroxysmal hemicrania and headache associated with vascular disorders.
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- Pyridine derived agents for cardiovascular diseases
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STR1 Compounds of formula (I) or a biolabile ester thereof, or a pharmaceutically acceptable salt of either, wherein Rl, R2, R3 and R4 are each independently selected from H or C1 -C4 alkyl; R5 is (CH2)m SO2 R6, (CH2)m NHSO2 R6 or (CH2)m NHCOR7 ; R6 and R7 are C1 -C6 alkyl, C1 -C3 perfluoroalkyl(CH2)n, C3 -C6 cycloalkyl(CH2)n, aryl(CH2)n or heteroaryl(CH2)n ; or R6 is NR8 R9 ; R8 is H or C1 -C4 alkyl; R9 is C1 -C6 alkyl, C3 -C6 cycloalkyl(CH2)n, aryl(CH2)n or heteroaryl(CH2)n ; or R8 and R9 together with the nitrogen atom to which they are attached form a 5- to 7-membered heterocyclic ring which may optionally incorporate a carbon-carbon double bond or a further hetero atom linkage selected from O, S, NH, N(C1 -C4 alkyl) and N(C1 -C5 alkanoyl), and which may optionally be substituted with one to three substituents each independently selected from C1 -C4 alkyl and C1 -C4 alkoxy, and which may optionally be benzo-fused; X is CH2, CHCH3, C(OH)CH3, C=CH2 or O; m is 0 or 1; n is 0, 1, 2 or 3; and Het is 3- or 4-pyridyl or 1-imidazolyl; with the proviso that when Het is 1-imidazolyl then X is CH2 or CHCH3, are combined thromboxane A2 synthetase inhibitors and thromboxane A2 /endoperoxide antagonists of utility in the treatment of disease conditions in which thromboxane A2 is a causative agent.
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- Reactions of β-Lactones with Potassium Alkoxides and Their Complexes with 18-Crown-6 in Aprotic Solvents
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The mechanism of the reaction of β-lactones (2-oxetanones) with potassium alkoxides in aprotic solvents was investigated.Despite previous suggestions, the attack of alkoxide ion occurs on the carbonyl carbon atom of β-lactones, cleaving the acyl-oxygen bond to yield the corresponding potassium alcoholate of the respective β-hydroxycarboxylic acid ester.Next, the unsaturated ester is formed due to potassium hydroxide elimination.The nature of the alkoxide used and complexation of alkali metal cation by crown ether have no significant effect on the reaction course in aprotic solvents.
- Kurcok, Piotr,Jedlinski, Zbigniew,Kowalczuk, Marek
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p. 4219 - 4220
(2007/10/02)
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- The 'Baylis - Hillman reaction' mechanism and applications revisited
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It is shown that reaction of aryl, benzyl, alkyl and functionalised alkyl acrylic esters with benzaldehyde, in the presence of 1,4-diazabicyclo[2.2.2] octane, strongly depends upon the electronic and steric effects of the ester part. This influence is also observed in condensation of furfuraldehyde. Moreover, for the first time, it is shown that the overall condensation is equilibrated.
- Fort, Yves,Berthe, Marie Christine,Caubere, Paul
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p. 6371 - 6384
(2007/10/02)
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- High solids acrylic coating systems
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High solids acrylic coating compositions are formulated by using as a reactive diluent, a low molecular weight hydroxyl-containing acrylic polymer. These polymers are prepared at about 15°-20° C. with anionic initiator concentrations greater than about 5 mole percent.
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- Formation of Iodides and Esters from Alcohols and Tributyldiiodophosphorane and Diiodotriphenylphosphorane
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Tributyldiiodophosphorane and diiodotriphenylphosphorane, prepared in situ from the corresponding phosphine and iodine, are generally able to convert primary and secondary alcohols into iodides at room temperature in diethyl ether or benzene containing two equivalents of hexamethylphosphoric triamide.Tertiary alcohols, as gauged by the lack of the reactivity of t-butyl alcohol, are, however, inert to this iodinating agents. 6-Hydroxyhexanoic acid yields a mixture of 6-iodohexanoic acid and 7-heptanolide.The first reagent also promotes facile condensation of secondaryand tertiary alcohols with carboxylic acids to form hindered esters in good yields.The phosphorane derived from tris(dimethylamino)phosphine and iodine, while less effective as an iodinating agent, rapidly converts 6-hydroxyhexanoic acid into 6-iodo-N,N-dimethylhexanamide, and hexanoic and benzoic acids into the corresponding N,N-dimethylamides in excellent yields at room temperature.Treatment of 3β-tosylocholest-5-ene with lithium iodide yields 3β-iodocholest-5-ene, and not 3α-iodocholest-5-ene, as previously reported.
- Haynes, Richard K.,Holden, Malcolm
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p. 517 - 524
(2007/10/02)
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