- Preparation method of acrylamido
-
The present invention relates to a method for preparing a pyrimidine, 9-fluorenone as raw material, by open loop, acid chloride, amidation, chlorination, Hofmann (Hofmann) rearrangement degradation to give 2-(4'-chlorophenyl) aniline, and then condensed with 2-chloronicotinamide to give the product acetoimide, the present invention also relates accordingly to the intermediates 4'-chloro-2-bibenzamide and 4'-chloro-2-aminobiphenyl preparation method. The method of the present invention can obtain the target product with high yield, high purity, and can reduce costs while reducing environmental harm.
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-
-
- Pd-Catalysed Suzuki-Miyaura cross-coupling of aryl chlorides at low catalyst loadings in water for the synthesis of industrially important fungicides
-
The Suzuki-Miyaura coupling reaction of electron-poor aryl chlorides in the synthesis of crop protection-relevant active ingredients in water is disclosed. Optimisation of the reaction conditions allowed running the reaction with 50 ppm of Pd-catalyst loading without an additional organic solvent in the cross-coupling reaction step in short reaction times. The system was optimised for the initial cross-coupling step of the large scale produced fungicides Boscalid, Fluxapyroxad and Bixafen up to 97% yield. It is also shown that the Suzuki-Miyaura reaction can be easily scaled up to 50 g using a simple product separation and purification using environmentally benign solvents in the work-up. To show the usability of this method, it was additionally applied in the three-step synthesis of the desired active ingredients.
- Goetz, Roland,Hashmi, A. Stephen K.,Orecchia, Patrizio,Petkova, Desislava Slavcheva,Rominger, Frank,Schaub, Thomas
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p. 8169 - 8180
(2021/11/01)
-
- Synthesis and process optimization of Boscalid by catalyst Pd-PEPPSI-IPrDtBu-An
-
The purpose of this research was to reduce the amount of noble metal palladium catalyst and improve the catalytic performance in the Suzuki–Miyaura cross-coupling reaction, which is the key step in the synthesis of Boscalid. Taking o-bromonitrobenzene and p-chlorophenylboronic acid as raw materials, three kinds of Pd-PEPPSI-IPr catalysts were synthesized and employed in the Suzuki reaction, and then the biaryl product was subjected to reduction and condensation reaction to give Boscalid. Under the optimal reaction conditions, the result showed that the catalytic system exhibits highest catalytic efficiency under aerobic conditions, giving the 2-(4-chlorophenyl)nitrobenzene in over 99 % yield. Moreover, the Pd-PEPPSI-IPrDtBu-An catalyst was minimized to 0.01 mol%. The synthesis process was mild, the post-treatment was simple, and the production cost was reduced, which makes it suitable for industrial production.
- Xu, Jian,Lan, Xiao-Bing,Xia, Lin-Jian,Yang, Yi,Cao, Gao
-
p. 247 - 256
(2021/05/06)
-
- Highly efficient palladium-catalyzed cross-coupling of diarylborinic acids with arenediazoniums for practical diaryl synthesis
-
A highly efficient cross-coupling of cost-effective diarylborinic acids with both isolatable and latent arenediazoniums, i.e. tetrafluoroborates and aryltriazenes, respectively, has been developed with a practical palladium catalyst system under base-free conditions in open flask at room temperature. A variety of electronically and sterically various biaryls, in particular, those bearing a coordinative ortho-substituent, could be obtained in good to excellent yields by using 0.3 mol% palladium acetate as catalyst. Features of the protocol including cost-effectiveness of diarylborinic acids, efficacy to heteroatom ortho-substituted substrates and high chemoselectivity to aryl chlorides have been clearly demonstrated in practical synthesis of fungicide Boscalid.
- Wang, Fengze,Wang, Chen,Sun, Guoping,Zou, Gang
-
-
- A Sustainable 1-Pot, 3-Step Synthesis of Boscalid Using Part per Million Level Pd Catalysis in Water
-
Boscalid is an active ingredient in several fungicides marketed by the BASF. Literature approaches use multipot processes, organic solvents, and unsustainable levels of palladium catalysis. Herein is disclosed a 1-pot, 3-step route using nanomicelles in water as the reaction medium and a very low loading (700 ppm or 0.07 mol %) of costly and endangered Pd. The sequence developed involves an initial Suzuki-Miyaura cross-coupling, the product from which is not isolated. The second step relies on a carbonyl iron powder (CIP) reduction of the aryl nitro group, followed by the third and final step involving an acylation with the required 2-chloronicotinyl chloride. The overall isolated yield for these three steps is 83%.
- Takale, Balaram S.,Thakore, Ruchita R.,Mallarapu, Rushil,Gallou, Fabrice,Lipshutz, Bruce H.
-
p. 101 - 105
(2019/12/30)
-
- Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
-
The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
- Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
-
supporting information
p. 4087 - 4101
(2019/04/30)
-
- Catalyst shuttling enabled by a thermoresponsive polymeric ligand: Facilitating efficient cross-couplings with continuously recyclable ppm levels of palladium
-
A polymeric monophosphine ligand WePhos has been synthesized and complexed with palladium(ii) acetate [Pd(OAc)2] to generate a thermoresponsive pre-catalyst that can shuttle between water and organic phases, with the change being regulated by temperature. The structure of the polymeric ligand was confirmed with matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry and size-exclusion chromatography (SEC) analysis, as well as nuclear magnetic resonance (NMR) measurements. This polymeric metal complex enables highly efficient Pd-catalyzed cross-couplings and tandem reactions using 50 to 500 ppm palladium, and this can facilitate reactions that are tolerant to a broad spectrum of (hetero)aryl substrates and functional groups, as demonstrated with 73 examples with up to 99% isolated yields. Notably, 97% Pd remained in the aqueous phase after 10 runs of catalyst recycling experiments, as determined via inductively coupled plasma-atomic emission spectrometry (ICP-AES) measurements, indicating highly efficient catalyst transfer. Furthermore, a continuous catalyst recycling approach has been successfully developed based on flow chemistry in combination with the catalyst shuttling behavior, allowing Suzuki-Miyaura couplings to be conducted at gram-scales with as little as 10 ppm Pd loading. Given the significance of transition-metal catalyzed cross-coupling and increasing interest in sustainable chemistry, this work is an important step towards the development of a responsive catalyst, in addition to having high activity, by tuning the structures of the ligands using polymer science.
- Wang, Erfei,Chen, Mao
-
p. 8331 - 8337
(2019/09/30)
-
- Visible-Light-Promoted, Catalyst-Free Gomberg-Bachmann Reaction: Synthesis of Biaryls
-
Biaryls were synthesized via a novel visible-light-promoted Gomberg-Bachmann reaction that does not require a photosensitizer or any metal reagents. The formation of an electron donor-acceptor complex between aryl diazonium salts and pyridine allows, under visible-light irradiation, the synthesis of biaryls in moderate-to-high yields.
- Lee, Juyoung,Hong, Boseok,Lee, Anna
-
p. 9297 - 9306
(2019/08/12)
-
- Process for synthesizing boscalid
-
The invention discloses a process for synthesizing boscalid. The process comprises the following steps: (1) coupling o-chlorobenzonitrile with benzene to obtain 2-cyanobiphenyl, then carrying out chlorination, reduction and salt formation purification to obtain 4'-chloro-2-aminobiphenyl hydrochloride; (2) carrying out condensation reaction on the prepared 4'-chloro-2-aminobiphenyl hydrochloride and 2-chloronicotinoyl chloride to obtain the boscalid. The process for synthesizing the boscalid has the advantages of simple synthesis process, no need of complex aftertreatment, cheap and easily available basic chemical raw materials, and suitability for industrial production.
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-
-
- Method for preparing boscalid
-
The invention relates to a method for preparing boscalid. The method comprises the following steps: sequentially preparing intermediates 2-(4-chlorophenyl)aniline and 2-chloronicotinyl chloride by means of a chlorination/ring opening reaction, an amidation reaction, Hofmann rearrangement and an acylating chlorination reaction, and enabling the obtained intermediates to be subjected to a syntheticreaction to obtain the boscalid. The method for preparing the boscalid has the advantages of being easy in obtaining of raw materials, easy in creation of reaction conditions, little in environmentalpollution and high in yield, thus being suitable for large-scale production.
- -
-
-
- A new,: Substituted palladacycle for ppm level Pd-catalyzed Suzuki-Miyaura cross couplings in water
-
A newly engineered palladacycle that contains substituents on the biphenyl rings along with the ligand HandaPhos is especially well-matched to an aqueous micellar medium, enabling valued Suzuki-Miyaura couplings to be run not only in water under mild conditions, but at 300 ppm of Pd catalyst. This general methodology has been applied to several targets in the pharmaceutical area. Multiple recyclings of the aqueous reaction mixture involving both the same as well as different coupling partners is demonstrated. Low temperature microscopy (cryo-TEM) indicates the nature and size of the particles acting as nanoreactors. Importantly, given the low loadings of Pd invested per reaction, ICP-MS analyses of residual palladium in the products shows levels to be expected that are well within FDA allowable limits.
- Takale, Balaram S.,Thakore, Ruchita R.,Handa, Sachin,Gallou, Fabrice,Reilly, John,Lipshutz, Bruce H.
-
p. 8825 - 8831
(2019/10/16)
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- Dingding acid radical fungus amine preparation method
-
A preparation method of boscalid comprises following steps: o-iodoaniline and 2-chloronicotinyl chloride have a condensation reaction to produce an intermediate product 2-chloro-N-(2-iodophenyl)pyridine-3-formamide;2-chloro-N-(2-iodophenyl)pyridine-3-formamide which is not purified has a Suzuki coupling reaction with 4-chlorophenylboronic acid directly, and boscalid is produced. A Ni/C preparation method is provided, and Ni/C is taken as a catalyst for the Suzuki coupling reaction, so that the production cost is greatly reduced; further, production raw materials are available, the yield is high, and the preparation method of boscalid is applicable to large-scale industrial production.
- -
-
Paragraph 0022; 0023; 0025; 0026; 0027
(2018/10/02)
-
- PROCESS FOR PREPARATION OF BOSCALID ANHYDRATE FORM I AND BOSCALID ANHYDRATE FORM II
-
The present invention relates to a novel process for preparation of boscalid anhydrate form I and boscalid anhydrate form II.
- -
-
Page/Page column 9; 10
(2018/04/17)
-
- PROCESS FOR PREPARATION OF BOSCALID
-
A process for the preparing of the crystalline modification II of the anhydrate of boscalid is provided, the process comprising (i) reacting 2-chloro-nicotinoyl chloride with 4'-chloro-biphenyl-2-ylamine in a solvent system while removing from the reaction mixture hydrogen chloride formed during the reaction; and (ii) recovering the crystalline modification II of the anhydrate of boscalid from the reaction mixture produced in step (i).
- -
-
Paragraph 0041; 0042; 0046; 0049; 0050; 0051
(2018/03/28)
-
- A dingding acid radical fungus amine synthesis process
-
The invention relates to a technical field of chemical synthesis, in particular to a process for synthesizing dingding acid radical fungus amine, to chlorine monobromo-benzene and O-such as nitrobenzene raw material through the reaction, layered, desolvation, filtering and washing such as synthetic dingding acid radical fungus amine a plurality of steps, compared with the prior art, beneficial effect of the invention: this invention adopts the synthetic route to the routine by reaction of the chemical reaction, mild reaction conditions, the operation is simple, and is suitable for industrial; at the same time to the chlorine monobromo-benzene as raw materials are synthetic dichlorobenzothiazole boric acid, 2 - (4 - chlorophenyl) nitrobenzene, 2 - (4 - chlorophenyl) aniline and dingding acid radical fungus amine synthetic route, higher yields.
- -
-
Paragraph 0012
(2019/01/07)
-
- PROCESS FOR PREPARING BOSCALID
-
A process for preparing the crystalline modification II of the anhydrate of boscalid is provided, the process comprising providing a solution of boscalid in an organic solvent system, heating the solution to an elevated temperature, and precipitating solid boscalid from the solution, the elevated temperature being sufficient to preferentially form the crystalline modification II of the anhydrate of boscalid.
- -
-
Paragraph 0055-0059
(2018/03/01)
-
- A 2 - chloro - N - (4' - chloro biphenyl - 2 - yl) nicotinamide synthetic method
-
The invention discloses a synthetic method of 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide. The method comprises the following steps: by taking o-chloronitrobenzene and 4-chlorobenzene boric acid as raw materials, performing Suzuki coupling reaction to generate a intermediate 4'-chloro-2-nitryldiphenyl; subsequently reducing to generate a intermediate 4'-chloro-2-aminodiphenyl; finally condensing the intermediate 4'-chloro-2-nitryldiphenyl and the intermediate 4'-chloro-2-aminodiphenyl with 2-chloronicotinoyl chloride to obtain a target product 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide. The method is used for preparing the 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide and has the advantages of mild reaction condition, simple process, low cost, high yield and the like.
- -
-
-
- A unified strategy for silver-, base-, and oxidant-free direct arylation of C-H bonds
-
Here, we report a dual catalytic approach for room temperature direct arylation of C-H bonds with aryldiazonium salts as a simple aryl group donor, also working as an internal oxidant via C-N2 bond cleavage. This unified strategy has been achieved by the synergistic combination of visible-light metal-free photoredox and palladium catalysis under silver-, base- and/or additive-free conditions. The broad substrate scope, functional group tolerance, excellent regioselectivity and redox-neutral conditions of this process make it attractive for the effective synthesis of a wide range of important N-heterocyclic commodities such as dibenzo[b,d]azepine, carbazole and phenanthridine.
- Sahoo, Manoj K.,Midya, Siba P.,Landge, Vinod G.,Balaraman, Ekambaram
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p. 2111 - 2117
(2017/07/24)
-
- The use of the arylhydrazine synthetic amino of the biphenyl method
-
The present invention describes a method for synthesising 2-aminobiphenyls and derivatives thereof. This method can be performed cost-effectively and is based on selective reactions. Functionalised biphenyl compounds are of great interest, particularly as pharmaceuticals and agricultural chemicals, and as precursors for such active ingredients. The method for producing a compound of formula 3 is characterised in that a compound of formula 1 is reacted with a compound of formula 2 in the presence of an oxidising agent.
- -
-
Paragraph 0394-0396
(2017/10/28)
-
- Preparation method of boscalid
-
The invention discloses a preparation method of boscalid. The method comprises the following steps: preparation of a 2-(4-chlorphenyl) aniline intermediate, namely dissolving chlorophenylboronic acid, o-iodoaniline, benzaldehyde and a catalyst into a first solvent, stirring, adding a sodium carbonate solution for reflux reaction, cooling, standing and layering to obtain an organic phase, adding an acid to the obtained organic phase, standing, layering, adjusting the pH value of the organic phase by using alkali, carrying out extraction through an extraction agent, drying through a drying agent, concentrating the first solvent and re-crystallizing to obtain the 2-(4-chlorphenyl) aniline; and preparation of the boscalid, namely dissolving the 2-(4-chlorphenyl) aniline intermediate and triethylamine into a second solvent to obtain a mixed solution, slowly adding the organic solvent of 2-chloronicotinoyl chloride to the mixed solution at a room temperature, separating out the organic phase, evaporating the second solvent from filtrate, obtaining a crude product and re-crystallizing to obtain the boscalid. The method has the advantages of being short in reaction route, simple in operation and high in yield.
- -
-
Paragraph 0017; 0018; 0019
(2017/10/22)
-
- A method for preparing boscalid
-
The invention relates to the field of compound preparation, particularly a preparation method of a novel bactericide boscalid. The method comprises the following steps: in a polar aprotic solvent or high boiling solvent, carrying out Suzuki reaction on a palladium catalyst p-chlorophenylboric acid and o-acetaminobrombenzene in the presence of alkali and quaternary ammonium salt to obtain an intermediate product 4'-chloro-2-acetaminobiphenyl; and deprotecting the intermediate product in the presence of concentrated hydrochloric acid, and condensing with 2-chloronicotinoyl chloride. According to the method, the Pd(OH)2/C is used as the catalyst to perform the Suzuki coupling reaction, and is recovered and reutilized many times; and thus, compared with the prior art, the method provided by the invention greatly saves the catalyst cost, is convenient for recovering the catalyst, and avoids using the high-cost raw material o-iodoaniline.
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-
-
- A method of preparing boscalid (by machine translation)
-
The invention relates to a method of preparing boscalid. The 2-chloro-N-(2-chlorophenyl) pyridine-3-carboxamide with the paradichlorbenzene boric acid added to the reactor, a catalyst is added, ligand 2-double cyclohexyl phosphine -2 ˊ, 6 ˊ-dimethoxy biphenyltetrazole (S-Phos), alkali, solvent/water system is a solvent, heating 100-140 °C reaction, containing boscalid obtained. Method for preparing boscalid of the present invention, short reaction steps, the operation is simple, low cost of raw materials easy to purchase, the yield is higher. The molar ratio of raw materials for the: 2-chloro-N-(2-chlorophenyl) pyridine-3-carboxamide: the paradichlorbenzene boric acid: catalyst: 2-double cyclohexyl phosphine -2 ˊ, 6 ˊ-dimethoxy biphenyltetrazole: alkali: solvent: water = 1 : (1.3-1.8) : (0.01-0.07) : (0.05-0.13) : (1-3) : (90-122) : (200-244). (by machine translation)
- -
-
Paragraph 0034; 0035
(2016/10/27)
-
- Amine Activation: Synthesis of N-(Hetero)arylamides from Isothioureas and Carboxylic Acids
-
A novel method for N-(hetero)arylamide synthesis based on rarely explored amine activation, rather than classical acid activation, is reported. The activated amines are easily prepared using a three-component reaction with commercial reagents. The new method shows a broad scope including challenging amides not (efficiently) accessible via classical protocols.
- Zhu, Yan-Ping,Sergeyev, Sergey,Franck, Philippe,Orru, Romano V. A.,Maes, Bert U. W.
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p. 4602 - 4605
(2016/09/28)
-
- Cationic Pd(II)-catalyzed C-H activation/cross-coupling reactions at room temperature: Synthetic and mechanistic studies
-
Cationic palladium(II) complexes have been found to be highly reactive towards aromatic C-H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN)4](BF4)2 or a nitrile-free cationic palladium(II) complex generated in situ from the reaction of Pd(OAc)2 and HBF4, effectively catalyzes C-H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C-H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1) C-H activation to generate a cationic palladacycle; (2) reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3) regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II) complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied.
- Nishikata, Takashi,Abela, Alexander R.,Huang, Shenlin,Lipshutz, Bruce H.
-
p. 1040 - 1064
(2016/07/06)
-
- A selective synthesis method boscalid different crystal forms
-
The invention relates to a selective synthesis method of cyprosulfamide with different crystal forms, and especially a selective synthesis method of cyprosulfamide with melting points of 143-45 DEG C (crystal form I) or 147-148 DEG C (crystal form II) by the selecting of mixing modes and adjusting stirring rate and cooling rate. The method is of great value in industrial production.
- -
-
Paragraph 0038; 0039
(2016/10/07)
-
- Recyclable glucose-derived palladium(0) nanoparticles as in situ-formed catalysts for cross-coupling reactions in aqueous media
-
In situ-generated, glucose-derived palladium(0) nanoparticles were shown to be convenient and effective catalysts for aqueous Mizoroki-Heck, Sonogashira and Suzuki-Miyaura cross-coupling reactions. The addition of only 4-10 mol% glucose to the reaction mixture lead to a significant increase in yield of the desired products in comparison to processes that omitted the renewable sugar. Interestingly, the Mizoroki-Heck reaction was observed to proceed in good yield even as the reaction reached acidic pH levels. Extensive analysis of the size and morphology of the in situ-formed palladium nanoparticles using advanced analytical techniques showed that the zero valent metal was surrounded by hydrophilic hydroxyl groups. The increased aqueous phase affinity afforded by these groups allowed for facile recycling of the catalyst.
- Camp, Jason E.,Dunsford, Jay J.,Dacosta, Oliver S. G.,Blundell, Rebecca K.,Adams, James,Britton, Joshua,Smith, Robert J.,Bousfield, Thomas W.,Fay, Michael W.
-
p. 16115 - 16121
(2016/02/20)
-
- One-pot synthesis of n-aryl-nicotinamides and diarylamines based on a tunable smiles rearrangement
-
A one-pot Smiles rearrangement has been developed as a useful protocol for the straightforward synthesis of diverse N-aryl-nicotinamides. This method also provides chemoselective access toward diarylamines based on the different substitutions of the amide group. The potential application of the transformation is exemplified by the synthesis of an on-market succinate dehydrogenase inhibitor, boscalid. A substituent-mediated Smiles rearrangement to N-aryl-nicotinamides and diarylamines has been developed. In addition to the wide range of heterocyclic building blocks, the one-pot process also provides an efficient access to an on-market fungicide, boscalid.
- Liu, Shihui,Zhu, Shaofan,Wu, Ying,Gao, Jiayu,Qian, Pengfei,Hu, Yanwei,Shi, Linsen,Chen, Shaohua,Zhang, Shilei,Zhang, Yinan
-
p. 3048 - 3052
(2015/05/13)
-
- Palladium Nanoparticles Supported on Sulfonic Acid Functionalized Silica as Trifunctional Heterogeneous Catalysts for Heck and Suzuki Reactions
-
The arylation of acrylates and boronic acids with anilines, through in situ generated aryl diazonium salts, was successfully achieved by using trifunctional heterogeneous catalysts bearing Br?nsted acid and metal active sites. The trifunctional materials were prepared by adsorption of palladium nanoparticles, generated by reduction of a solution of Pd(OAc)2 onto a commercially available sulfonic acid functionalized silica. These new trifunctional catalysts act as a 1) proton donor for the diazotization step, 2) counterion for the diazonium salt, and 3) Pd source for the coupling step. This unprecedented strategy, features mild and safe conditions as hazardous aryl diazonium salts are generated in situ and only produces environmentally friendly byproducts such as tBuOH, H2O, and N2.
- Oger, Nicolas,Le Grognec, Erwan,Felpin, Fran?ois-Xavier
-
p. 2085 - 2094
(2015/11/24)
-
- Synthesis of secondary amides from N-Substituted amidines by tandem oxidative rearrangement and isocyanate elimination
-
In this work an efficient tandem process transforming N-substituted amidines into secondary amides has been described. The process involves N-acylurea formation by reaction of the substrate with bis(acyloxy)(phenyl)-λ3-iodane followed by isocyanate elimination. The periodinane reagents are obtained from the commercially available phenyl-iodine(III) diacetate [PhI(OAc)2, (PIDA)] by ligand exchange with carboxylic acids. The N-substituted amidine substrates are easily synthesized from readily available nitriles. The method is applicable for secondary amide synthesis, based on both aliphatic and (hetero)aromatic amines, including challenging amides consisting of sterically hindered acids and amines. Moreover, the protocol allows one to combine steric bulk with electron deficiency in the target amides (aniline based). Such compounds are difficult to synthesize efficiently based on classical condensation reactions involving carboxylic acids and amines. Overall, the synthetic protocol transforms a nitrile into a secondary amide in both aliphatic and (hetero)aromatic systems.
- Debnath, Pradip,Baeten, Mattijs,Lefvre, Nicolas,Van Daele, Stijn,Maes, Bert U. W.
-
p. 197 - 209
(2015/03/03)
-
- Three-component coupling based on flash chemistry. Carbolithiation of benzyne with functionalized aryllithiums followed by reactions with electrophiles
-
A flow microreactor method for three-component coupling of benzyne was developed based on flash chemistry. o-Bromophenyllithium generated from 1-bromo-2-iodobenzene and a functionalized aryllithium generated from the corresponding aryl halide were mixed at -70 °C. In the subsequent reactor o-bromophenyllithium is decomposed to generate benzyne without affecting the functionalized aryllithium at -30 °C, and carbolithiation of benzyne with the aryllithium took place spontaneously. The resulting functionalized biaryllithium was reacted with an electrophile in the subsequent reactor to give the corresponding three-component coupling product. The precise optimization of reaction conditions using the temperature-residence time mapping is responsible for the success of the present transformation. The present method has been successfully applied to the synthesis of boscalid.
- Nagaki, Aiichiro,Ichinari, Daisuke,Yoshida, Jun-Ichi
-
supporting information
p. 12245 - 12248
(2014/11/08)
-
- Process for the Synthesis of Aminobiphenylene
-
The present invention relates to a process for the synthesis of 2-aminobiphenylene and derivatives thereof by reacting a benzene diazonium salt with an aniline compound under basic reaction conditions.
- -
-
Paragraph 0393; 0394; 0395; 0396
(2014/02/15)
-
- Palladium nanoparticles on graphite oxide: A recyclable catalyst for the synthesis of biaryl cores
-
The synthesis of life saving drug molecules in a cost-effective and environmentally benign pathway is of paramount significance. We present an environment friendly protocol to prepare core moieties of top selling drug molecules such as boscalid and telmisartan using Suzuki-Miyaura coupling conditions. In contrast to the traditional synthesis of these pharmaceutically important molecules, we have accomplished a graphite oxide (GO) supported palladium nanoparticles (PdNPs) based catalyst which quantitatively produced these core biaryl moieties of top selling drug molecules in a recyclable way. The catalytic activity remained unchanged even after 16 successive catalytic cycles without incorporating any palladium metal impurity in the pharmaceutically significant organic products. A detailed study including IR spectroscopy, solid state NMR spectroscopy, X-ray photoelectron spectroscopy, and DFT calculation was employed to understand the role of solid support on the nondecaying recycling ability of the catalyst during the Suzuki-Miyaura coupling reaction. The study indicates a strong chemical interaction of the different functionalities present in the GO, with the palladium centers which is primarily responsible for such sustained catalytic activity during the consecutive Suzuki-Miyaura coupling cycles.
- Santra, Subhankar,Hota, Pradip Kumar,Bhattacharyya, Rangeet,Bera, Parthasarathi,Ghosh, Prasenjit,Mandal, Swadhin K.
-
p. 2776 - 2789
(2014/01/06)
-
- The gomberg-bachmann reaction for the arylation of anilines with aryl diazotates
-
Simply aqueous sodium hydroxide is sufficient to exclude ionic side reactions and to prepare 2-aminobiphenyls from aryl diazotates and anilines through a new variant of the Gomberg-Bachmann reaction (see scheme). The metal-free reaction under basic conditions allows to exploit the highly radical-stabilizing effect of the aniline's free amino function for the first time, which leads to a so far unreached regioselectivity. Copyright
- Pratsch, Gerald,Wallaschkowski, Tina,Heinrich, Markus R.
-
supporting information
p. 11555 - 11559,5
(2012/12/12)
-
- The gomberg-bachmann reaction for the arylation of anilines with aryl diazotates
-
Simply aqueous sodium hydroxide is sufficient to exclude ionic side reactions and to prepare 2-aminobiphenyls from aryl diazotates and anilines through a new variant of the Gomberg-Bachmann reaction (see scheme). The metal-free reaction under basic conditions allows to exploit the highly radical-stabilizing effect of the aniline's free amino function for the first time, which leads to a so far unreached regioselectivity. Copyright
- Pratsch, Gerald,Wallaschkowski, Tina,Heinrich, Markus R.
-
supporting information
p. 11555 - 11559
(2013/01/14)
-
- Method for Producing Aminobiphenylene
-
The present invention relates to a process for preparing substituted 2-aminobiphenyls and to a process for preparing (Het)arylamides of such 2-aminobiphenyls.
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-
Page/Page column 24-25
(2011/05/08)
-
- Method For Manufacturing Aryl Carboxamides
-
A process for preparing arylcarboxamides of the formula (I) where Ar =a mono- to trisubstituted phenyl, pyridyl or pyrazolyl ring, where the substituents are selected from halogen, Ci-C4-alkyl and C1-C4-haloalkyl; M =thienyl or phenyl, which may bear a halogen substituent; Q =direct bond, cyclopropylene, fused bicycio[2.2.1]heptane or bicyclo[2.2.1]heptene ring; R1 =hydrogen, halogen, C1-C6-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, mono- to trisubstituted phenyl, where the substituents are selected from halogen and trifluoromethylthio, or cyclopropyl; by reacting an acid chloride of the formula (II) with an arylamine (III) in a suitable nonaqueous solvent, wherein, in the absence of an auxiliary base, a) the acid chloride (II) is initially charged, b) a pressure of from 0 to 700 mbar is established, c) the arylamine (III) is metered in in an approximately stoichiometric amount and d) the product of value is isolated.
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Page/Page column 4
(2011/04/14)
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- Selective Mg insertion into substituted mono- and dichloro arenes in the presence of LiCl: A new preparation of boscalid
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The LiCl-mediated Mg insertion into polysubstituted aryl chlorides bearing up to three chloro substituents in ortho or meta position selectively leads to Grignard reagents which readily react with various electrophiles. As an application, we have developed a new formal synthesis of boscalid. Georg Thieme Verlag Stuttgart - New York.
- Dunst, Cora,Knochel, Paul
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experimental part
p. 2064 - 2068
(2011/10/09)
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- Toward a continuous-flow synthesis of Boscalid
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A two-step continuous-flow protocol for the synthesis of 2-amino-4′-chlorobiphenyl, a key intermediate for the industrial preparation of the fungicide Boscalid is described. Initial tetrakis(triphenylphosphine)palladium-catalyzed high-temperature Suzuki-Miyaura cross-coupling of 1-chloro-2-nitrobenzene with 4-chlorophenylboronic acid in a microtubular flow reactor at 160°C using the tert-butanol/water/potassium tert-butoxide solvent/base system provides 4′-chloro-2-nitrobiphenyl in high yield. After in-line scavenging of palladium metal with the aid of a thiourea-based resin, subsequent heterogeneous catalytic hydrogenation is performed over platinum-on-charcoal in a dedicated continuous-flow hydrogenation device. The overall two-step homogeneous/heterogeneous catalytic process can be performed in a single operation providing the desired 2-amino-4′- chlorobiphenyl in good overall yield and high selectivity. Copyright
- Glasnov, Toma N.,Kappe, C. Oliver
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experimental part
p. 3089 - 3097
(2011/02/22)
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- Improved Suzuki-Miyaura reactions of aryldiazonium salts with boronic acids by tuning palladium on charcoal catalyst properties
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An improved Suzuki-Miyaura cross-coupling reaction of aryldiazonium tetrafluoroborates with boronic acids catalyzed by a highly active palladium catalyst supported on charcoal is described as an extremely practical and efficient protocol. A properties-activity study of various catalysts clearly established that the optimal catalytic activity was obtained with palladium nanoparticles having a low oxidation degree and uniformly dispersed on the charcoal. The optimized reaction conditions allow the cross-coupling to proceed at room temperature without any base and ligand in technical grade methanol. Although the catalyst could not be recycled, the low palladium contamination of the solvent and product after a simple filtration of the palladium on charcoal (Pd/C) renders the present protocol competitive and safer for the environment compared to more conventional homogeneous conditions. We have highlighted the efficiency of this novel protocol by a short synthesis of the fungicide Boscalid
- Felpin, Francois-Xavier,Fouquet, Eric,Zakri, Cecile
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experimental part
p. 649 - 655
(2009/12/08)
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- Synthesis of amino- and hydroxybiphenyls by radical chain reaction of arenediazonium salts
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Radically shortened: In the propagation step of the title reaction, the cyclohexadienyl radical intermediate is oxidized by an arenediazonium ion to give the biaryl product (see scheme) while simultaneously a new aryl radical and nitrogen are formed. (Chemical Equation Presented).
- Wetzel, Alexander,Ehrhardt, Varinia,Heinrich, Markus R.
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experimental part
p. 9130 - 9133
(2009/02/08)
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- Synergistic Fungidical Active Substance Combinations
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The present invention relates to novel active substance combinations which contain spiroxamine, which is known, a known azole and a known carboxamide and which are very suitable for controlling undesired phytopathogenic fungi.
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- Light-fluorous safety-catch arylgermanes - Exceptionally robust, photochemically activated precursors for biaryl synthesis by Pd(0) catalysed cross-coupling
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A new class of arylgermane derivative that participate efficiently in Pd(0)-catalysed cross-coupling reactions with aryl bromides following photochemical activation is described. The Royal Society of Chemistry.
- Spivey, Alan C.,Tseng, Chih-Chung,Hannah, Joseph P.,Gripton, Christopher J. G.,De Fraine, Paul,Parr, Nigel J.,Scicinski, Jan J.
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p. 2926 - 2928
(2008/03/11)
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- NOVEL CRYSTALLINE MODIFICATION OF THE ANHYDRATE OF BOSCALID
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The invention relates to monoclinic 2-chloro-N-(4'-chlorobiphenyl-2-yl)-nicotinamide of formula (I), which melts at a temperature of between 147 and 148 °C, and to a method for producing the same.
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Page/Page column 5
(2008/06/13)
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