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One-step Conversion of Amides and Esters to Acid Chlorides with PCl3
A general and efficient iodine-promoted chlorination of amides and esters with phosphorus trichloride is described. For the first time. Various inactivated amides including secondary and tertiary amides were directly converted to the corresponding acid chlorides in one-step. The substrate scope of methyl esters including aromatic and aliphatic esters was also explored under this system. This method is simple, scalable and wide in scope, which provides an approach to preparation of these acid chlorides.
Li, Fangshao,Wu, Xiaofang,Guo, Fengzhe,Tang, Zi-Long,Xiao, Jing
supporting information
p. 4314 - 4317
(2021/07/16)

Remarkably Efficient Iridium Catalysts for Directed C(sp2)-H and C(sp3)-H Borylation of Diverse Classes of Substrates
Here we describe the discovery of a new class of C-H borylation catalysts and their use for regioselective C-H borylation of aromatic, heteroaromatic, and aliphatic systems. The new catalysts have Ir-C(thienyl) or Ir-C(furyl) anionic ligands instead of the diamine-type neutral chelating ligands used in the standard C-H borylation conditions. It is reported that the employment of these newly discovered catalysts show excellent reactivity and ortho-selectivity for diverse classes of aromatic substrates with high isolated yields. Moreover, the catalysts proved to be efficient for a wide number of aliphatic substrates for selective C(sp3)-H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C-H bonds. A number of late-stage C-H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)-H and C(sp3)-H borylations enabling the method more general. Preliminary mechanistic studies suggest that the active catalytic intermediate is the Ir(bis)boryl complex, and the attached ligand acts as bidentate ligand. Collectively, this study underlines the discovery of new class of C-H borylation catalysts that should find wide application in the context of C-H functionalization chemistry.
Chattopadhyay, Buddhadeb,Hassan, Mirja Md Mahamudul,Hoque, Md Emdadul
supporting information
p. 5022 - 5037
(2021/05/04)

Immobilization of (l)-valine and (l)-valinol on SBA-15 nanoporous silica and their application as chiral heterogeneous ligands in the Cu-catalyzed asymmetric allylic oxidation of alkenes
SBA-15 nanoporous silica was synthesized by hydrothermal method using P123 surfactant and tetraethoxyortosilicate in acidic condition and then functionalized by 3-chloropropyltrimethoxysilane. Next, by immobilization of chiral amino acid (S)-2-amino-3-methyl butanoic acid (l-valine) and chiral amino alcohol (S)-2-amino-3-methylbutane-1-ol (l-valinol), preparedviathe reduction ofl-valine by NaBH4/I2in THF, on functionalized-SBA-15, chiral heterogeneous ligands AL*-i-Pr-SBA-15 and AA*-i-Pr-SBA-15 were prepared and characterized by FT-IR, XRD, TGA, EDX, SEM, BET-BJH techniques. The asymmetric allylic oxidation of alkenes was done using copper-complexes of these ligands and the as-synthesized peresters. The reactions were optimized by varying various parameters such as temperature, solvent, amount of chiral heterogeneous ligand, as well as the type and amount of copper salt. Under optimized conditions, 6 mg of AL*-i-Pr-SBA-15 and 3.2 mol% of Cu(CH3CN)4PF6in acetonitrile at 50 °C, the chiral allylic ester was obtained with 80% yield and 39% enantiomeric excess in 24 h. The recyclability of the chiral heterogeneous catalysts was also evaluated without significant reduction in the reaction results up to three runs.
Samadi, Saadi,Ashouri, Akram,Rashid, Hersh I,Majidian, Shiva,Mahramasrar, Mahsa
supporting information
p. 17630 - 17641
(2021/10/04)

Butyrylcholine esterase selective inhibitor as well as preparation method and application thereof
The invention discloses a butyrylcholine esterase selective inhibitor as well as a preparation method and application thereof. The inhibitor is a compound shown as a formula (I). The invention also discloses application of the compound in preparation of d
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Paragraph 0035; 0039-0040

(2021/06/22)

Photochemical Activation of Aromatic Aldehydes: Synthesis of Amides, Hydroxamic Acids and Esters
A cheap, facile and metal-free photochemical protocol for the activation of aromatic aldehydes has been developed. Utilizing thioxanthen-9-one as the photocatalyst and cheap household lamps as the light source, a variety of aromatic aldehydes have been activated and subsequently converted in a one-pot reaction into amides, hydroxamic acids and esters in good to high yields. The applicability of this method was highlighted in the synthesis of Moclobemide, a drug against depression and social anxiety. Extended and detailed mechanistic studies have been conducted, in order to determine a plausible mechanism for the reaction.
Nikitas, Nikolaos F.,Apostolopoulou, Mary K.,Skolia, Elpida,Tsoukaki, Anna,Kokotos, Christoforos G.
supporting information
p. 7915 - 7922
(2021/05/03)

PCl3-mediated transesterification and aminolysis of tert-butyl esters via acid chloride formation
A PCl3-mediated conversion of tert-butyl esters into esters and amides in one-pot under air is developed. This novel protocol is highlighted by the synthesis of skeletons of bioactive molecules and gram-scale reactions. Mechanistic studies revealed that this transformation involves the formation of an acid chloride in situ, which is followed by reactions with alcohols or amines to afford the desired products.
Wu, Xiaofang,Zhou, Lei,Li, Fangshao,Xiao, Jing
p. 491 - 497
(2021/01/20)

Photo-on-Demand Synthesis of Vilsmeier Reagents with Chloroform and Their Applications to One-Pot Organic Syntheses
The Vilsmeier reagent (VR), first reported a century ago, is a versatile reagent in a variety of organic reactions. It is used extensively in formylation reactions. However, the synthesis of VR generally requires highly toxic and corrosive reagents such as POCl3, SOCl2, or COCl2. In this study, we found that VR is readily obtained from a CHCl3 solution containing N,N-dimethylformamide or N,N-dimethylacetamide upon photo-irradiation under O2 bubbling. The corresponding Vilsmeier reagents were obtained in high yields with the generation of gaseous HCl and CO2 as byproducts to allow their isolations as crystalline solid products amenable to analysis by X-ray crystallography. With the advantage of using CHCl3, which bifunctionally serves as a reactant and a solvent, this photo-on-demand VR synthesis is available for one-pot syntheses of aldehydes, acid chlorides, formates, ketones, esters, and amides.
Liang, Fengying,Eda, Kazuo,Okazoe, Takashi,Wada, Akihiro,Mori, Nobuaki,Konishi, Katsuhiko,Tsuda, Akihiko
p. 6504 - 6517
(2021/05/06)

Reaction pathway change on plasmonic Au nanoparticles studied by surface-enhanced Raman spectroscopy
Gold nanoparticles (Au NPs) are nanoscale sources of light and electrons, which are highly relevant for their extensive applications in the field of photocatalysis. Although a number of research works have been carried out on chemical reactions accelerated by the energetic hot electrons/holes, the possibility of reaction pathway change on the plasmonic Au surfaces has not been reported so far. In this proof-of-concept study, we find that Au NPs change the reaction pathway in photooxidation of alkyne under visible light irradiation. This reaction produces benzil ([sbnd]CO[sbnd]CO[sbnd]) without the presence of Au NPs. In contrast, as indicated by surface-enhanced Raman spectroscopic (SERS) results, the C[sbnd]C triple bonds ([sbnd]C[tbnd]C[sbnd]) adsorbed on Au NPs are converted into carboxyl ([sbnd]COOH) and acyl chloride ([sbnd]COCl) groups. The plasmonic Au NPs not only provide energetic charge carriers but also activate the reactant molecules as conventional heterogeneous catalysts. This study discloses the second role of plasmonic NPs in photocatalysis and bridges the gap between plasmon-driven and conventional heterogeneous catalysis.
Li, Ran,Zhang, Can-Can,Wang, Dan,Hu, Yan-Fang,Li, Yong-Long,Xie, Wei
supporting information
p. 2846 - 2850
(2021/05/29)

Preparation method of benzoyl chloride compound
The invention provides a preparation method of a benzoyl chloride compound. The preparation method comprises the following step: with a trichloromethyl benzene compound and a benzoic acid compound as raw materials and ferric oxide as a catalyst, carrying out a catalytic reaction to prepare the benzoyl chloride compound. According to the method disclosed by the invention, the benzoyl chloride compound can be obtained under the condition of not using a solvent, yield is up to 95% or above, atom economy is good, cost is lower, operation is simpler, more convenient and safer, the treatment amount of three wastes is smaller, the three wastes is easier to treat, and the method is more suitable for industrial production.
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Paragraph 0037-0053

(2021/06/22)

Preparation method of 3-chloropropionyl chloride
The invention provides a preparation method of 3-chloropropionyl chloride, wherein the preparation method comprises the following steps: mixing acrylic acid with a certain amount of catalyst, dropwise adding a certain amount of trichlorotoluene at a certain temperature under the protection of nitrogen, reacting for a period of time, and performing vacuum rectification to respectively obtain 3-chloropropionyl chloride and benzoyl chloride. The preparation method has the following beneficial effects: 1) acrylic acid and trichlorotoluene are adopted as raw materials, 3-chloropropionyl chloride is prepared in the presence of a catalyst, and benzoyl chloride with wide application is produced as a byproduct; the reaction route is environment-friendly, the process is simple, no emission is generated, and the requirement of atom economy is met; and the technical problem that toxic raw materials are used in the prior art is solved, and the technical problem that by-products polluting the environment are possibly generated in the prior art is also solved; and 2) the method is low in production cost, and in addition, the reaction route is combined with the specific reaction conditions, so that the yield of the obtained product is quite high and reaches 95% or above.
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Paragraph 0019-0021

(2021/10/27)

Carbon dots as photocatalysts for organic synthesis: Metal-free methylene-oxygen-bond photocleavage
We report for the first time that irradiation of four different citric acid-derived carbon dots (CDs), in the absence of any other redox mediators, promotes an organic reaction. In this proof-of-concept study methylene-oxygen bond reductive photocleavage in N-methyl-4-picolinium esters is demonstrated. Cyclic voltammetry and UV-Vis spectra of the CDs and of the esters indicate that photocleavage reactivity correlates with the redox properties and the relative energies expressed in the Fermi scale. A photo-fragmentation mechanism is proposed. This study offers a new possibility to employ inexpensive and readily available CDs to promote photo-organic reactions.
Cailotto, Simone,Negrato, Matteo,Daniele, Salvatore,Luque, Rafael,Selva, Maurizio,Amadio, Emanuele,Perosa, Alvise
supporting information
p. 1145 - 1149
(2020/03/11)

A practical chlorination of tert-butyl esters with PCl3 generating acid chlorides
For the first time, using PCl3, a range of tert-butyl esters is chlorinated successfully, allowing access of both aromatic acid chlorides and aliphatic acid chlorides in good yields. The method features simple reaction conditions and wide substrate scope. Various tert-butyl esters including aryl esters, alkenyl esters, and alkyl esters were tolerated well in the reaction. A plausible mechanism is proposed.
Wu, Xiaofang,Zhou, Lei,Yang, Ruoqi,Guo, Fengzhe,Tang, Zi-Long,Xiao, Jing
p. 301 - 304
(2020/01/29)

A Versatile Approach to Dynamic Amide Bond Formation with Imine Nucleophiles
Dynamic covalent chemistry has rapidly become an important approach to access supramolecular structures. While the products generated in these reactions are held together by covalent bonds, the reversible nature of the transformations can limit the utility of many these systems in creating robust materials. We describe herein a method to form stable and commonly employed amide bonds by exploiting the reversible coupling of imines and acyl chlorides. The reaction employs easily accessible reagents, is dynamic under ambient conditions, without catalysts, and can be trapped with simple hydrolysis. This offers an approach to create broad families of amide products under thermodynamic control, including the selective formation of amide macrocycles or polymers.
Arndtsen, Bruce A.,Erguven, Huseyin,Keyzer, Evan N.
supporting information

(2020/05/05)

Preparation method of amlodipine intermediate
The invention provides a preparation method of an amlodipine intermediate, belonging to the technical field of bulk drug synthesis. The preparation method comprises the following steps: mixing a compound 1 (2-(2-(2-hydroxyethoxy)ethyl)isoindoline-1,3-dione), an N-O free radical catalyst, a metal salt catalyst and a first organic solvent, and carrying out an oxidation reaction under the action of an oxidizing agent to obtain a compound 2, wherein the oxidizing agent is air or oxygen; mixing the compound 2, an acylating chlorination reagent and a second organic solvent, and carrying out an acylating chlorination reaction to obtain a compound 3; and mixing the compound 3, monopotassium malonate, tertiary amine and a third organic solvent, and carrying out a C-acylation reaction to obtain theamlodipine intermediate. The method provided by the invention has the advantages of usage of cheap and easily available raw materials, less three-waste pollution, high process safety, simplicity and convenience in operation and easiness in industrial production.
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(2020/09/16)

Palladium-Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide
An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.
Bismuto, Alessandro,Boehm, Philip,Morandi, Bill,Roediger, Sven
supporting information
p. 17887 - 17896
(2020/08/19)

Preparation method of 2,4,6-trimethylbenzoyl chloride and acyl chloride co-production technology
The invention relates to the field of new materials of fine chemicals, in particular to 2,4,6-trimethylbenzoyl chloride (also known as trimesoyl chloride) and an environment-friendly and economical novel preparation process technology for co-producing series acyl chloride products.
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Paragraph 0021-0023

(2020/11/25)

Synthetic process for benzoyl chloride
The invention relates to a synthetic process for benzoyl chloride, and belongs to the technical field of preparation of the benzoyl chloride. The synthetic process comprises the following steps: (1) adding a side reaction inhibitor under irradiation of an LED light source, introducing chlorine gas into toluene, and performing a reaction to obtain crude benzotrichloride, wherein the wavelength of the LED light source is 520-650 nm, and the side reaction inhibitor is a mixture of 4,6-dinitro-2-sec-butylphenol and aniline; (2) adding benzoic acid, adding the crude benzotrichloride obtained in thestep (1) dropwise under the action of a catalyst, and performing a reaction at 110-120 DEG C to obtain crude benzoyl chloride; and (3) performing reduced-pressure distillation purification on the crude benzoyl chloride obtained in the step (2) to obtain the refined benzoyl chloride. The synthetic process provided by the invention has the advantages of simple operation, a short reaction period, alow reaction temperature, low energy consumption, a high product yield, high product purity and low production costs, and is suitable for industrialized production.
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Paragraph 0029; 0031; 0032; 0034; 0035; 0037; 0038; 0040

(2019/07/16)

Synthesis and in vitro anti-platelet aggregation activities of 2-methoxy-5-arylamido-N-(pyridin-3-yl-methyl)benzamides
In order to discover novel compounds with anti-platelet aggregation activities, a series of novel 2-methoxy-5-arylamido-N-(pyridin-3-ylmethyl)benzamides (1a–n) were synthesized and their anti-platelet aggregation activities were evaluated by the turbidimetric method in response to the following agonists: adenosine diphosphate (ADP) (5 mM/L), arachidonic acid (AA) (20 μM/L), and collagen (1 mg/mL). Those synthesized compounds that have better in vitro activities were subjected to cell toxicity tests via cell counting kit-8 (CCK-8) assay. The biological evaluation revealed that compound 1a (IC50: 0.21 μM/L) exhibited the highest anti-platelet aggregation activities when ADP was selected as an inducer, and compound 1b (IC50: 0.23 μM/L) showed the best activities when AA was selected as inducer, and compound 1m (inhibition rate: 55.06%) had significant anti-platelet aggregation activities when collagen was selected as inducer among all target compounds. Moreover, the effect of cell toxicity exhibited that none of the compounds had obvious cell toxicity against L929 cells. Therefore, 2-methoxy-5-arylamido-N-(pyridin-3-ylmethyl)benzamides have the potential to become a novel kind of anti-platelet drugs and deserve further study.
Wang, Yan,Wang, Xiao,Chen, Xin,Liu, Xiujie
(2018/12/11)

Formamide catalyzed activation of carboxylic acids-versatile and cost-efficient amidation and esterification
A novel, broadly applicable method for amide C-N and ester C-O bond formation is presented based on formylpyrrolidine (FPyr) as a Lewis base catalyst. Herein, trichlorotriazine (TCT), which is the most cost-efficient reagent for OH-group activation, was employed in amounts of ≤40 mol% with respect to the starting material (100 mol%). The new approach is distinguished by excellent cost-efficiency, waste-balance (E-factor down to 3) and scalability (up to >80 g). Moreover, high levels of functional group compatibility, which includes acid-labile acetals and silyl ethers, are demonstrated and even peptide C-N bonds can be formed. In comparison to reported amidation procedures using TCT, yields are considerably improved (for instance from 26 to 91%) and esterification is facilitated for the first time in synthetically useful yields. These significant enhancements are rationalized by activation by means of acid chlorides instead of less electrophilic acid anhydride intermediates.
Huy, Peter H.,Mbouhom, Christelle
p. 7399 - 7406
(2019/08/20)

Preparation method of aromatic acyl chloride
The invention discloses a preparation method of aromatic acyl chloride. An aromatic acyl chloride compound is prepared through a reaction of aryl carboxylic acid and phosphorus trichloride. The preparation method of the aromatic acyl chloride has the advantages that the phosphorus trichloride is taken as a chloride reagent, the corresponding acyl chloride is synthesized from the aryl carboxylic acid, so that the production cost is low, the operation is simple, a by-product is low in toxicity, the environmental friendliness is achieved, the yield is high, and the method is conductive to industrial production.
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Paragraph 0047-0050; 0091-0100

(2019/07/11)

Visible light-induced transformation of aldehydes to esters, carboxylic anhydrides and amides
A transition metal- and organophotocatalyst free synthesis of esters, carboxylic anhydrides and amides from aldehydes induced by visible-light has been reported. The proposed methodology can be carried out by the use of sunlight or artificial visible light as a blue LED source. The methodology has a very broad applicability and the desired products are obtained in very satisfactory yields.
Gaspa, Silvia,Raposo, Inês,Pereira, Leonor,Mulas, Gabriele,Ricci, Pier Carlo,Porcheddu, Andrea,De Luca, Lidia
supporting information
p. 10711 - 10715
(2019/07/15)

4,5-Diaryl 3(2H)Furanones: Anti-inflammatory activity and influence on cancer growth
Apart from their anti-inflammatory action, COX inhibitors have gathered the interest of many scientists due to their potential use for the treatment and prevention of cancer. It has been shown that cyclooxygenase inhibitors restrict cancer cell growth and are able to interact with known antitumor drugs, enhancing their in vitro and in vivo cytotoxicity. The permutation of hydrophilic and hydrophobic aryl groups in COX inhibitors leads to cardinal changes in the biological activity of the compounds. In the present study, thirteen heterocyclic coxib-like 4,5-diarylfuran-3(2H)-ones and their annelated derivatives-phenanthro[9,10-b]furan-3-ones-were synthesized and studied for anti-inflammatory and COX-1/2 inhibitory action and for their cytotoxic activity on the breast cancer (MCF-7) and squamous cell carcinoma (HSC-3) cell lines. The F-derivative of the -SOMe substituted furan-3(2H)-ones exhibited the best activity (COX-1 IC50 = 2.8 μM, anti-inflammatory activity (by carrageenan paw edema model) of 54% (dose 0.01 mmol/kg), and MCF-7 and HSC-3 cytotoxicity with IC50 values of 10 μM and 7.5 μM, respectively). A cytotoxic effect related to the COX-1 inhibitory action was observed and a synergistic effect with the anti-neoplastic drugs gefitinib and 5-fluorouracil was found. A phenanthrene derivative exhibited the best synergistic effect with gefitinib.
Semenok, Dmitrii,Medvedev, Jury,Giassafaki, Lefki-P.,Lavdas, Iason,Vizirianakis, Ioannis S.,Eleftheriou, Phaedra,Gavalas, Antonis,Petrou, Anthi,Geronikaki, Athina
(2019/05/24)

Co(ii)-cluster-based metal-organic frameworks as efficient heterogeneous catalysts for selective oxidation of arylalkanes
To explore metal-organic frameworks (MOFs) based on Co-clusters as heterogeneous catalysts to selectively catalyze the reaction of C-H bond oxidation of aromatic alkanes to their corresponding ketones, three MOFs {[Co5(pmbcd)2(μ3-OH)2(H2O)4(DMF)2]·4DMF}n (MOF 1), {[Co2(pmbcd)(bpea)2]·2H2O·2DMF}n (MOF 2), and {[Co2(pmbcd)(dpp)2]·3H2O·2DMF}n (MOF 3) (H4pmbcd = 9,9′-(1,4-phenylenebis(methylene))bis(9H-carbazole-3,6-dicarboxylic acid), bpea = 1,2-bis(4-pyridyl)ethane, dpp = 1,3-di(4-pyridyl)propane) were successfully synthesized and structurally characterized. MOF 1 was constructed from a pentanuclear Co(ii) cluster and exhibited a porous framework with channels of 8 × 10 ?2 along the b axis. MOF 2 was constructed from [Co2(CO2)4] units and presented a porous three-dimensional (3D) framework with channels of 11 × 13 ?2 along the b axis and of 10 × 12 ?2 along the c axis. MOF 3 was a flat two-dimensional (2D) layer based on binuclear Co(ii) units when dpp as an auxiliary ligand was introduced. The Co5-cluster-based MOF 1 exhibited excellent catalytic activity for the direct C-H bond activation of arylalkanes to ketones in H2O under room temperature because of its high density of Lewis acidic sites within the frameworks and suitable channel size to access the catalytic sites. It also presented the spatial confinement effect and catalyzed the reaction with high regioselectivity, forming mono-ketones as the sole products. Easy product separation, simple reaction procedures, and recyclability of these catalysts make the catalytic system attractive. Our work highlights the superiority of the MOF-based materials as heterogeneous catalysts.
Fan, Yanru,Li, Xiao,Gao, Kuan,Liu, Yu,Meng, Xiangru,Wu, Jie,Hou, Hongwei
p. 1666 - 1673
(2019/03/07)

Preparation and synthesis process for benzoyl chloride
The invention relates to the field of preparation of chemical products, especially to the field of preparation of benzoyl chloride. Benzoyl chloride is an important organic synthesis intermediates andis extensively applied to the synthesis of pesticides, pharmaceuticals, dyes, perfumes, additives, etc. Benzoyl chloride is also an important benzoylation and benzylation reagent and is mainly used for the production of benzoyl peroxide, benzophenone, benzyl benzoate, benzyl cellulose, benzamide and other important chemical raw materials.
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Paragraph 0004

(2018/03/01)

Preparation methods of acyl chloride and thioxanthone
The present invention relates to the field of fine chemicals and pharmaceutical chemicals, particularly to new economical preparation process technologies of ortho-chlorosulfenyl aroyl chloride and thioxanthone compounds, and applications of the thioxanthone compounds in synthesis of photoinitiators or other new material chemicals.
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Paragraph 0015

(2018/04/01)

Iron(iii)-catalyzed selective N-O bond cleavage to prepare tetrasubstituted pyridines and 3,5-disubstituted isoxazolines from: N -vinyl-α,β-unsaturated ketonitrones
An iron(iii)-catalyst controlled cyclization and selective N-O bond cleavage of N-vinyl-α,β-unsaturated nitrones has been achieved under mild conditions to access tetrasubstituted pyridines and 3,5-disubstituted isoxazolines in moderate to good yields. The tetrasubstituted pyridines were afforded with FeCl3 as a catalyst while using FeCl3·6H2O combined with 1,10-phenanthroline delivered isoxazolines. The regioselectivity for cyclization of styrenyl groups in N-vinyl-α,β-unsaturated nitrones was completely different during the formation of pyridines and isoxazolines. A rational mechanism for the formation of pyridines and isoxazolines was proposed based on the further control experimental studies. The isoxazolines can be converted to a novel bidentate N-ligand over four steps and an epoxypyridine scaffold was obtained from N-vinyl nitrone when copper(ii) acetate in combination with the prepared bidentate N-ligand was used.
Chen, Chun-Hua,Wu, Qing-Yan,Wei, Cui,Liang, Cui,Su, Gui-Fa,Mo, Dong-Liang
p. 2722 - 2729
(2018/06/29)

Functional Group Transposition: A Palladium-Catalyzed Metathesis of Ar-X σ-Bonds and Acid Chloride Synthesis
We describe the development of a new method to use palladium catalysis to form functionalized aromatics: via the metathesis of covalent σ-bonds between Ar-X fragments. This transformation demonstrates the dynamic nature of palladium-based oxidative addition/reductive elimination and offers a straightforward approach to incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited to assemble acid chlorides without the use of high energy halogenating or toxic reagents and, instead, via the metathesis of aryl iodides with other acid chlorides.
De La Higuera Macias, Maximiliano,Arndtsen, Bruce A.
supporting information
p. 10140 - 10144
(2018/08/23)

Metathesis-active ligands enable a catalytic functional group metathesis between aroyl chlorides and aryl iodides
Current methods for functional group interconversion have, for the most part, relied on relatively strong driving forces which often require highly reactive reagents to generate irreversibly a desired product in high yield and selectivity. These approaches generally prevent the use of the same catalytic strategy to perform the reverse reaction. Here we describe a catalytic functional group metathesis approach to interconvert, under CO-free conditions, two synthetically important classes of electrophiles that are often employed in the preparation of pharmaceuticals and agrochemicals—aroyl chlorides (ArCOCl) and aryl iodides (ArI). Our reaction design relies on the implementation of a key reversible ligand C–P bond cleavage event, which enables a non-innocent, metathesis-active phosphine ligand to mediate a rapid aryl group transfer between the two different electrophiles. Beyond enabling a practical and safer approach to the interconversion of ArCOCl and ArI, this type of ligand non-innocence provides a blueprint for the development of a broad range of functional group metathesis reactions employing synthetically relevant aryl electrophiles.
Lee, Yong Ho,Morandi, Bill
p. 1016 - 1022
(2018/09/06)

CLEAN PROCESS FOR PREPARING CHLOROFORMYL-SUBSTITUTED BENZENE
Clean process for preparing a chloroformyl-substituted benzene by oxidation of a tail gas hydrogen chloride from a chlorination reaction and a chloroacylation reaction and recycling of the resulting oxidation product chlorine gas into the chlorination reaction. The present invention provides a clean process for preparing a polymer-grade chloroformyl-substituted benzene.
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Paragraph 0126; 0140; 0151; 0163

(2017/12/17)

Nickel-catalysed direct alkylation of thiophenes via double C(sp3)-H/C(sp2)-H bond cleavage: The importance of KH2PO4
A Ni-catalyzed oxidative C-H/C-H cross-dehydrogenative coupling (CDC) reaction was developed for constructing various highly functionalized alkyl (aryl)-substituted thiophenes. This method employs thiophenes and aliphatic (aromatic) amides that contain an 8-aminoquinoline as a removable directing group in the presence of a silver oxidant. The approach enables the facile one-step synthesis of substituted thiophenes with high functional group compatibility via double C-H bond cleavage without affecting C-Br and C-I bonds. DFT calculations verify the importance of KH2PO4 as an additive for promoting C-H bond cleavage and support the involvement of a Ni(iii) species in the reaction.
Wang, Xie,Xie, Peipei,Qiu, Renhua,Zhu, Longzhi,Liu, Ting,Li, You,Iwasaki, Takanori,Au, Chak-Tong,Xu, Xinhua,Xia, Yuanzhi,Yin, Shuang-Feng,Kambe, Nobuaki
p. 8316 - 8319
(2017/07/26)

Anhydrides from aldehydes or alcohols via oxidative cross-coupling
A novel type of metal-free oxidative cross-coupling for the synthesis of symmetrical and mixed anhydrides from aldehydes or benzylic alcohols has been developed. The aldehydes or alcohols were converted in situ into their corresponding acyl chlorides, which were then reacted with an array of carboxylic acids. The methodology has a general applicability, and was successfully employed to prepare either aromatic or aliphatic symmetrical anhydrides and mixed anhydrides, which are very unstable compounds.
Gaspa, Silvia,Amura, Ida,Porcheddu, Andrea,De Luca, Lidia
supporting information
p. 931 - 939
(2017/02/10)

Metal-free oxidative self-coupling of aldehydes or alcohols to symmetric carboxylic anhydrides
A metal-free synthesis of symmetrical anhydrides has been developed starting from aldehydes, both aliphatic and aromatic or primary benzylic alcohols. The reaction occurs at room temperature and makes use of trichloroisocyanuric acid (TCCA) as an oxidant providing the desired carboxylic anhydrides in satisfactory yields.
Gaspa, Silvia,Porcheddu, Andrea,De Luca, Lidia
supporting information
p. 2533 - 2536
(2017/06/13)

RECYCLABLE CATALYSTS FOR CHLORINATION OF ORGANIC ACIDS AND ALCOHOLS
The present invention discloses recyclable polymeric catalyst of Formula I, for chlorination of organic acids and alcohols using chlorinating agents such as carbonyl chloride, oxalyl chloride or thionyl chloride, wherein, ‘m’ on the pendent groups on polystyrene backbone can have values from 1 to 5 and R is the alkyl group ranging from C1 to C5.
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Paragraph 0101

(2017/10/10)

Nitrogen mustard derivative N,N-di(2-chloroethyl)-N'-benzoyl-1,4-phenylenediamine and preparation method thereof
The invention particularly discloses a structural formula of a nitrogen mustard derivative N,N-di(2-chloroethyl)-N'-benzoyl-1,4-phenylenediamine, and a preparation method thereof. The preparation method comprises the following steps: preparing N,N-di(2-chloroethyl)-1,4-phenylenediamine; putting the N,N-di(2-chloroethyl)-1,4-phenylenediamine, dichloromethane and triethylamine into a reactor, cooling in ice-water bath, stirring, dropwise adding a mixed solution of benzoyl chloride and dichloromethane into the reactor, removing the ice-water bath after addition, conducting reaction at room temperature for 8 to 14 hours, sequentially performing washing, drying and normal-pressure distillation on the reaction liquid after the reaction is conducted completely, and purifying the distilled filter cake to obtain the product. The arylamine nitrogen mustard derivative provided by the invention can effectively reduce the toxic and side effects of nitrogen mustard on the premise of enhancing the treatment index of the nitrogen mustard, and has sterilization and inflammation-diminishing curative effects to reduce the risk of complication caused by the fact that the immunity is reduced after a patient is subjected to chemical therapy.
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Paragraph 0055; 0056; 0068; 0069; 0081; 0082

(2017/08/28)

A copper-catalyzed Ritter-type cascade via iminoketene for the synthesis of quinazolin-4(3H)-ones and diazocines
We have developed a copper-catalyzed Ritter-type reaction/cyclization cascade of anthranilic acids and nitriles, affording the quinazolin-4(3H)-ones. The cascade proceeds through a Ritter-type reaction capturing the iminoketene intermediates by nitriles. Furthermore, we found a novel Ritter-type reaction/condensation/intramolecular anti-Markovnikov hydroamination cascade, providing access to functionalized diazocines in one-pot.
Abe, Takumi,Kida, Koshiro,Yamada, Koji
p. 4362 - 4365
(2017/04/21)

METHOD FOR PREPARATION OF CARBOXYLIC ACID CHLORIDES FROM METHYL KETONES WITH TWO REAGENTS
The invention discloses a method for the preparation of carboxylic acid chlorides starting from methyl ketones with a sulfur chloride and a chlorinating reagent.
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Page/Page column 32

(2017/01/26)

The Conversion of tert-Butyl Esters to Acid Chlorides Using Thionyl Chloride
The reaction of tert-butyl esters with SOCl2 at room temperature provides acid chlorides in unpurified yields of 89% or greater. Benzyl, methyl, ethyl, and isopropyl esters are essentially unreactive under these conditions, allowing for the selective conversion of tert-butyl esters to acid chlorides in the presence of other esters.
Greenberg, Jacob A.,Sammakia, Tarek
p. 3245 - 3251
(2017/03/23)

A General Cp*CoIII-Catalyzed Intramolecular C?H Activation Approach for the Efficient Total Syntheses of Aromathecin, Protoberberine, and Tylophora Alkaloids
Herein, we report a Cp*CoIII-catalyzed C?H activation approach as the key step to create highly valuable isoquinolones and pyridones as building blocks that can readily be applied in the total syntheses of a variety of aromathecin, protoberberine, and tylophora alkaloids. This particular C?H activation/annulation reaction was achieved with several terminal as well as internal alkyne coupling partners delivering a broad scope with excellent functional group tolerance. The synthetic applicability of this protocol reported herein was demonstrated in the total syntheses of two Topo-I-Inhibitors and two 8-oxyprotoberberine cores that can be further elaborated into the tetrahydroprotoberberine and the protoberberine alkaloid core. Moreover these building blocks were also transformed to six different tylophora alkaloids in expedient fashion.
Lerchen, Andreas,Knecht, Tobias,Koy, Maximilian,Daniliuc, Constantin G.,Glorius, Frank
supporting information
p. 12149 - 12152
(2017/09/13)

Visible-Light-Accelerated C?H Sulfinylation of Heteroarenes
Heteroaromatic sulfoxides are a frequent structural motif in natural products, drugs, catalysts, and materials. We report a metal-free visible-light-accelerated synthesis of heteroaromatic sulfoxides from sulfinamides and peroxodisulfate. The reaction proceeds at room temperature with blue-light irradiation and allows the C?H sulfinylation of electron-rich heteroarenes, such as pyrroles and indoles. An electrophilic aromatic substitution mechanism is proposed based on the substrate scope, substitution selectivity, and competition experiments with different nucleophiles.
Meyer, Andreas Uwe,Wimmer, Alexander,K?nig, Burkhard
supporting information
p. 409 - 412
(2016/12/30)

Process for the preparation of benzoyl chloride
The invention relates to a preparation method of benzoyl chloride and belongs to the technical field of the preparation of the benzoyl chloride. The preparation method of the benzoyl chloride comprises the following steps: (1) under the irradiation of an LED light source, firstly, adding a side reaction inhibitor, and then introducing chlorine into methylbenzene, and performing a heating and stirring reaction to obtain the crude product of benzyl trichloride; (2) heating benzoic acid for melting, and in the presence of a catalyst, adding the crude product of the benzyl trichloride obtained in the step (1) for reacting to obtain the crude product of benzoyl chloride; (3) purifying the obtained crude product of the benzoyl chloride by virtue of reduced pressure distillation, thereby obtaining the refined benzoyl chloride. The preparation method of the benzoyl chloride is simple to operate, short in reaction period, low in energy consumption, high in product purity and yield, low in production cost and suitable for industrial production.
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Paragraph 0045; 0047

(2017/03/08)

Metal-Free Oxidative Cross Esterification of Alcohols via Acyl Chloride Formation
A novel metal-free oxidative cross esterification of alcohols has been achieved using trichloroisocyanuric acid as an oxidant. The alcohols were converted in situ into their corresponding acyl chlorides, which were then reacted with primary and secondary aliphatic, benzylic and allylic alcohols and phenols. A wide variety of esters was obtained in satisfactory yields.
Gaspa, Silvia,Porcheddu, Andrea,De Luca, Lidia
supporting information
p. 154 - 158
(2016/01/25)

Method for preparing acyl chloride by catalyzing phosgene and acid
The invention discloses a method for preparing acyl chloride by catalyzing phosgene and acid. The method includes the following steps that 1, with carboxylic acid as a raw material, a catalyst and a solvent are added, and under the condition that the temperature is maintained to range from 20 DEG C to 200 DEG C, phosgene is introduced into a reaction flask for a reaction; 2, after the molar ratio of carboxylic acid to phosgene reaches 1:1.0-1:10, phosgene introduction is stopped, reacted mixed liquor is obtained and filtered, obtained filter liquor is subjected to reduced pressure distillation at a high vacuum degree to obtain acyl chloride, and an obtained filter cake continues to serve as the catalyst in the step 1 to be recycled. Compared with an existing catalyst adopted for preparing acyl chloride according to a phosgene method, the catalyst used in the method is small in dosage, convenient to recycle, easy to separate from a product, better in product quality, safe, stable and environmentally friendly, generated solid waste is greatly reduced, the experience of operators is greatly improved, and safety risks are lowered.
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Paragraph 0073; 0074; 0075

(2016/10/20)

Preparation method of acyl chloride
The invention relates to a preparation method of acyl chloride. The method comprises the following steps that 1, carboxylic acid is added into a reactor, or carboxylic acid is dissolved in organic solvent, a device is connected, and the temperature is raised to 100 DGE C-250 DEG C; 2, phosgene is introduced into the reactor for a reaction, and then the temperature is decreased to room temperature; 3, nitrogen is introduced, residual phosgene and hydrogen chloride are cleaned away, reaction liquid which is reacted without solvent is subjected to decompression distillation and purification directly, and needed acyl chloride is obtained; reaction liquid which is reacted with the solvent is subjected to decompression distillation to remove the solvent, and needed acyl chloride is obtained. According to the preparation method of acyl chloride, no catalyst is added, the risks that in the synthesizing process, due to the fact that the catalyst is dissolved, color of the finial product of acyl chloride is increased, and the catalyst is remained in late products are avoided, after the reaction is finished, high-quality acyl chloride can be obtained through decompression distillation, and the technological process is simple; due to the fact that in the whole technological process, except for absorbable and available phosgene, hydrogen chloride and carbon dioxide, no other three waste is discharged, the preparation method of acyl chloride is environmentally friendly, and the good implement value is achieved.
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Paragraph 0056; 0057

(2016/11/28)

Visible-Light-Mediated Synthesis of Amides from Aldehydes and Amines via in Situ Acid Chloride Formation
An efficient visible-light photocatalysis-based one-pot amide synthesis method was developed; visible-light irradiation of a mixture of an aldehyde, tert-butyl hydrogen peroxide, and N-chlorosuccinimide using a Ru(bpy)3Cl2 photocatalyst afforded an acid chloride, which subsequently reacted with amine to yield the corresponding amide. The reaction was used to synthesize moclobemide and a D3 receptor intermediate.
Iqbal, Naeem,Cho, Eun Jin
p. 1905 - 1911
(2016/03/15)

METHOD FOR PREPARATION OF CARBOXYLIC ACID CHLORIDES FROM METHYL KETONES
The invention discloses a method for the preparation of carboxylic acid chlorides starting from methyl ketones with a sulfur chloride.
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Page/Page column 31; 33

(2017/01/02)

METHOD FOR PRODUCING a-HALO-TETRAACYL-GLUCOSE
There is provided an efficient and excellent preparation method of an α-halo-tetraacyl-glucose which is suitable for industrial preparation, which comprises reacting D-glucose or lower alkyl D-glucoside with a reactive derivative of a carboxylic acid and a metal halide to prepare the α-halo-tetraacyl-glucose represented by the formula (III): wherein R represents an optionally substituted lower alkyl group or an optionally substituted aryl group, and X represents a halogen atom, in one step, and the resulting α-halo-tetraacyl-glucose (III) can be converted into a compound of the formula (I) or a salt thereof by subjecting to a conventional method.
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(2016/01/29)

One-pot synthesis of amides from carboxylic acids activated using thionyl chloride
A one-pot synthesis of secondary and tertiary amides from carboxylic acids and amines by using SOCl2 has been developed. Also when sterically hindered amines were used as the starting materials, excellent yields of the corresponding amides were obtained. The amidation of N-protected α-amino acids with secondary amines proceeds effectively with good yields. The process works well also in the presence of acid sensitive groups and occurs with almost complete retention of stereochemical integrity of chiral substrates. This protocol could be extended to industrial large-scale production processes.
Leggio,Belsito,De Luca,Di Gioia,Leotta,Romio,Siciliano,Liguori
p. 34468 - 34475
(2016/06/13)

Mechanism of the Palladium-Catalyzed Synthesis of Münchnones: The Role of Ligands in N-Acyl Iminium Salt Carbonylation
The palladium-catalyzed carbonylative coupling of imines, acid chlorides, and dipolarophiles can provide efficient routes to prepare nitrogen-containing heterocycles. One challenge in developing this reaction, and in the creation of more active catalyst systems, is the lack of data on how this complex transformation proceeds. To address this, we report here the results of our mechanistic studies on this system, and in particular the formation of mesoionic münchnones. This includes the synthesis of key catalytic intermediates, model reactions, and kinetic studies that support the role of these compounds in catalysis. Together, these studies provide a clear picture of the impact of catalyst structure, ligands, and palladium nanoparticles on facilitating the carbonylation of in situ generated iminium salts, and suggest an avenue for the creation of more active catalyst systems.
Tjutrins, Jevgenijs,Dhawan, Rajiv,Lu, Yingdong,Arndtsen, Bruce A.
supporting information
p. 15945 - 15954
(2016/10/24)

Synthesis, characterization and microbial activity of new aryl esters of 1,1'-bis(4-hydroxyphenyl)cyclohexane
Aryl esters of 1,1'-bis(4-hydroxyphenyl)cyclohexane (bisphenol-C) were synthesized by condensing bisphenol-C with aryl acid chlorides using triethylamine as a catalyst and ethyl acetate as a solvent at room temperature.The compounds were characterized by
Patel, Chirag Bhupendra,Dhaduk, Bhavin Babu,Parsania, Parsotam Hari
p. 505 - 511
(2015/06/22)

Metal-Free Direct Oxidation of Aldehydes to Esters Using TCCA
Aromatic and aliphatic aldehydes are simply converted into esters by an efficient oxidative esterification carried out under mild conditions. The aldehydes are converted in situ into their corresponding acyl chlorides, which are then reacted with primary and secondary aliphatic, benzylic, allylic, and propargylic alcohols and phenols. A variety of esters are obtained in high yields.
Gaspa, Silvia,Porcheddu, Andrea,De Luca, Lidia
supporting information
p. 3666 - 3669
(2015/08/18)