Month: October 2022

Sathiyamoorthi, Sivakumar; Almansour, Abdulrahman I.; Raju, Suresh Kumar; Natarajan, Arumugam; Kumar, Raju Ranjith published the artcile< Imidazolium ylide mediated tandem Knoevenagel-Michael-O-cyclization sequence for the synthesis of multi-substituted 4,5-dihydrofurans>, Name: 3-(3-Chlorophenyl)-3-oxopropanenitrile, the main research area is benzoylacetonitrile benzaldehyde imidazolium ylide multicomponent tandem Knoevenagel Michael heterocyclization; diphenyl benzoyl dihydrofuran carbonitrile preparation diastereoselective.

The diastereoselective syntheses of novel trans aroyldiaryldihydrofurancarbonitriles I [R = H, 4-Me, 3-Cl, 4-Cl, X = H, 2-Cl, 3-Br, etc., Y = H, 4-F, 4-MeO, 4-Cl] have been achieved via a one-pot, three-component tandem protocol involving aroyl acetonitriles, aromatic aldehydes, and imidazolium ylides in the presence of Et3N.

Synthetic Communications published new progress about Acetophenones Role: RCT (Reactant), RACT (Reactant or Reagent). 21667-62-9 belongs to class nitriles-buliding-blocks, and the molecular formula is C9H6ClNO, Name: 3-(3-Chlorophenyl)-3-oxopropanenitrile.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Reutskaya, Elena; Osipyan, Angelina; Sapegin, Alexander; Novikov, Alexander S.; Krasavin, Mikhail published the artcile< Rethinking Hydrolytic Imidazoline Ring Expansion: A Common Approach to the Preparation of Medium-Sized Rings via Side-Chain Insertion into [1.4]Oxa- and [1.4]Thiazepinone Scaffolds>, Application of C7H3ClFN, the main research area is hydrolytic imidazoline ring expansion medium size ring synthesis.

The previously reported ring-expansion strategy involving hydrolytically prone imidazoline rings was thought to include the formation of a hydrated imidazoline intermediate. In this work, we accessed the latter via the addition of a 2-aminoethyl side chain onto a lactam moiety. This led to an efficient three-atom ring expansion of diarene-fused [1.4]oxazepines and [1.4]thiazepines and led us to propose to term this common approach the hydrated imidazoline ring expansion (HIRE) reaction. The strategy was extended to the insertion of longer (containing up to five atoms) side chains, and thus, larger (11- to 12-membered) diarene-fused rings were obtained via the homo-HIRE and homo2-HIRE reactions, resp. This underscores the utility of the HIRE reaction for the preparation of medium-sized rings, an important class of chem. tools for interrogation of various biol. targets.

Journal of Organic Chemistry published new progress about Aldehydes Role: RCT (Reactant), RACT (Reactant or Reagent) (reductive alkylation agents). 94087-40-8 belongs to class nitriles-buliding-blocks, and the molecular formula is C7H3ClFN, Application of C7H3ClFN.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Wu, Hai-Qiu; Yan, Zi-Hong; Chen, Wen-Xue; He, Qiu-Qin; Chen, Fen-Er; De Clercq, Erik; Balzarini, Jan; Daelemans, Dirk; Pannecouque, Christophe published the artcile< Towards new C6-rigid S-DABO HIV-1 reverse transcriptase inhibitors: Synthesis, biological investigation and molecular modeling studies>, Formula: C8H5F2N, the main research area is C6 rigid SDABO analog preparation HIV1 RT inhibitor; HIV-1 reverse transcriptase; NNRTIs; Rigid conformation; S-DABO; SAR.

A series of C6-rigid S-DABO analogs characterized by a substituted benzoyl group at C6 position of the pyrimidine ring has been synthesized and biol. evaluation as NNRTIs against wild-type HIV-1 strain IIIB, double RT mutant (K103N + Y181C) strain RES056 as well as HIV-2 strain ROD in MT-4 cell cultures. Most of the compounds exhibited moderate antiviral activities. Among them, compound 7q displayed the highest anti-HIV-1 activity with an EC50 value of 0.26 μM and a selectivity index (SI) of 541. The preliminary structure-activity relationship (SAR) of these new S-DABOs was investigated, the target RT was confirmed and docking study was performed.

Bioorganic & Medicinal Chemistry published new progress about Antiviral agents. 658-99-1 belongs to class nitriles-buliding-blocks, and the molecular formula is C8H5F2N, Formula: C8H5F2N.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Schaefer, Fred C.; Peters, Grace A. published the artcile< Base-catalyzed reaction of nitriles with alcohols. A convenient route to imidates and amidine salts>, Electric Literature of 6136-93-2, the main research area is .

The base-catalyzed reaction of nitriles with alcs. to form imidates was estimated as an attractive preparative method which was useful for a wide variety of electroneg. substituted aliphatic and aromatic nitriles. This reaction was used as the basis for a convenient procedure for the preparation of amidine salts. In general, 0.100 mole of the purified nitrile was mixed with MeOH, 0.010 mole NaOMe added, the solution diluted to 100 ml. at 25°, and liquors withdrawn at intervals, added to 0.100N HCl, and back titrated potentiometrically. In most cases, substantial conversion occurred within 0.5 hr. and the reaction was close to equilibrium in less than 24 hrs. The following results of comparative reactions were obtained under the standard conditions (nitrile, time in hrs., and % conversion to imidate given): NCCMe2CMe2CN, 22, 1; NC(CH2)4CN, 24, 1.5; MeCN, 2, 2; PhCH2CN, 24, 12; Et2NCH2CN, 48, 22; NC(CH2)2CN, 24, 69; BuOCH2OCHMeCN, 96, 86; [Et3NCH2CN]Cl, 48, 76; Me3COCH2CN, 30, 91; CH2:CClCN, 25, 90; MeCHClCN, 0.5, 91; CH2ClCN, 0.5, 93; (EtO)2CHCN, 1, 95; p-MeOC6H4CN, 96, 15; PhCN, 20, 20; p-ClC6H4CN, 48, 45; p-O2NC6H4CN, 8, 83; m-O2NC6H4CN, 4, 86; p-C6H4(CN)2, 7, 108; 3-(C5H4N)CN, 24, 71; (2-C5H4N)CN, 2, 97; Me2NCN, 24, 100 Et2NCN, 144, 100. Some nitriles gave no apparent imidate under the standard conditions. Titration of acid-hydrolyzed aliquots was carried out potentiometrically with 2 end points being observed (at pH 7 and 3.5). Addnl. experiments were carried out with p-O2NC6H4CN at different catalyst concentrations At 25° and 0.95M, the following equilibrium conversions were obtained: 0.050M NaOMe, 83%; 0.10M NaOMe, 81%; 0.20M NaOMe, 78%. (Effect of temperature). In 7 hrs. at 25°, 100 cc. MeOH containing 0.010 mole NaOMe dissolved 5.1 g. terephthalonitrile. Titration showed the presence of 0.042 mole of imidate. When the reaction mixture was heated 3 hrs. at 65°, the imidate content dropped to 0.025 mole; conversion 62.5%. In a similar experiment, it was shown that conversion to imidate in 0.04 M solution p-nitrobenzonitrile decreased from 80 to 50% on heating from 25° to 65°. The expected higher conversion at temperatures below 25° was noted with M p-chlorobenzonitrile in MeOH. When inert solvents were used the equilibrium conversions at 25° of p-nitrobenzonitrile were 13% in 90% C6H6 and 15% in 80% dioxane. With terephthalonitrile in 50% PhNO2, conversion was 19%; in 80% 2-methoxyethanol, 26%. With 2,2-diethoxyacetonitrile (I) as the standard reagent, a number of alcs. were studied with equilibria determined at 25°. The following results were obtained (R of ROH, and equilibrium conversion in % given): Me, 95; Me, 95; Me (3% H2O), 91; Et, 89; Pr, 82; Bu, 78; iso-Bu, 78; iso-Pr, 63. p-Nitrobenzonitrile (M) with anhydrous alc. containing 0.01M NaOMe gave 78% imidate at 25°. I (studied for reaction rate as a function of catalyst concentration) gave the following results (molar concentration of catalyst, k in min.-1, and k’ in l. mole-1 min.-1 given): 0.10, 0.098, 0.98; 0.071, 0.071, 0.99; 0.050, 0.048, 0.96. When KCN in MeOH was used as a catalyst, a clear solution was obtained after 120 hrs. with p-nitrobenzonitrile and in an addnl. 24 hrs. equilibrium was reached at 79% conversion. Cyanomethyltrimethylammonium chloride reacted normally with MeOH and KCN, although MeO- caused degradation. Isopropoxyacetonitrile (15 g.) and 0.5 g. NaOMe in 50 cc. MeOH was kept overnight at room temperature; titration indicated an 81% conversion and isolation gave 13.2 g. Me 2-isopropoxyacetimidate, b2 32-7°. 2-Cyanopyridine (26 g.) and 1.35 g. NaOMe in 225 cc. MeOH kept overnight at room temperature gave 31.4 g. Me pyridine-2-carboximidate, b23 118-22°. p-Nitrobenzonitrile (35 g.) and 100 cc. MeOH containing 1 g. NaOMe refluxed 4 hrs. gave 13.3 g. unchanged nitrile and 21.7 g. Me p-nitrobenzimidate, m. 75°, contaminated with some Me p-nitrobenzoate and p-nitrobenzamide. 2-Chloropropionitrile (65 g.) in 200 cc. alc. and 2.2 g. NaOMe kept 45 min. at 25° gave 53 g. Et 2-chloropropionimidate, b60 70-5°. Several amidine salts were prepared A MeOH solution of an imidate was treated with NH4Cl, the mixture stirred a few hrs. (reaction time 1-24 hrs.), solvent removed, and the product extracted with Et2O and recrystallized The following RC:NHNH2.HCl were thus prepared (R, molar concentration of original nitrile, molar concentration NaOMe catalyst, % yield, and m.p. given): CH2Cl, 2.5, 0.07, 96, 95-9°; MeCHCl, 3.1, 0.20, 73, 130-1°; Me3COCH2, 1.00, 0.10, 78, 157-9°; m-O2NC6H4, 1.00, 0.10, 80, 250-2°; p-O2NC6H4, 0.05, 0.050, 78, 285-7°; 3-C6H4N, 1.00, 0.10, 192-4°; 2-C5H4N, 1.00, 0.10, 95, 149-51°. In other work, excellent yields of amidine thiocyanates, acetates, and bromides were obtained by use of the appropriate ammonium salt. Terephthalonitrile (10 g.) and 100 cc. MeOH containing 0.50 g. NaOMe refluxed 2.5 hrs. and the hot solution added to 150 cc. ice H2O containing 12 cc. 12N HCl, kept overnight, and the product separated gave 61% Me p-cyanobenzoate, m. 59-61°. Di-Me terephthalate was expected to arise from the diimidate present, but could conceivably have been dissolved in the discarded aqueous MeOH.

Journal of Organic Chemistry published new progress about Alcohols Role: USES (Uses). 6136-93-2 belongs to class nitriles-buliding-blocks, and the molecular formula is C6H11NO2, Electric Literature of 6136-93-2.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Wang, Yu-Hao; Zhang, De-Hua; Cao, Ze-Hun; Li, Wang-Lai; Huang, Yi-Yong published the artcile< A formal [3 + 3] cycloaddition of allenyl imide and activated ketones for the synthesis of tetrasubstituted 2-pyrones>, Application In Synthesis of 21667-62-9, the main research area is pyrone preparation; allenyl imide ketoester cycloaddition; diketone allenyl imide cycloaddition; ketonitrile allenyl imide cycloaddition.

CsOH.H2O-catalyzed formal [3 + 3] cycloadditions of allenyl imide with β-ketoesters RC(O)CH2C(O)OR1 (R = Ph, cyclohexyl, 2-thienyl, Me, etc.; R1 = Me, Et), 1,3-diketones R2C(O)CH2R3 [R2 = Ph, 3-fluorophenyl, 2-iodophenyl, etc; R3 = C(O)C6H5, C(O)(3-CH3C6H4), C(O)(3-(CH3O)C6H4), C(O)(3-(CF3)C6H4)] or β-ketonitriles R2C(O)CH2R3 (R3 = CN) for the synthesis of tetrasubstituted 2-pyrone derivatives I, II have been demonstrated. The allenyl imide was utilized as a C3-synthon, and a ketenyl intermediate was proposed via the process of 1,4-addition of carbon anion to allene followed by elimination of the 2-oxazolidinyl group.

RSC Advances published new progress about [3+3] Cycloaddition reaction. 21667-62-9 belongs to class nitriles-buliding-blocks, and the molecular formula is C9H6ClNO, Application In Synthesis of 21667-62-9.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Boehme, Horst; Neidlein, Richard published the artcile< The cleavage of orthocarboxylic acid esters with acyl halides and acyl cyanides>, Name: 2,2-Diethoxyacetonitrile, the main research area is .

HC(OPh)3 (I) with acyl halides yields the corresponding carboxylic acid Ph esters and (PhO)2CHCl (II) which reacts readily with PhSH and with Me2NH. Orthocarboxylic acid esters, orthocarbonates, and acetals are cleaved by AcCN with the formation of carboxylic acid esters and derivatives of (EtO)2CHCN (III). I (2.9 g.) and 0.8 g. AcCl kept 5 days at room temperature under N, filtered, and distilled gave 1.1 g. PhOAc, b0.15 40-52°, n20D 1.5012, 1.4 g. II, b0.15 128-30°, and unchanged I, b0.15 175-7°, m. 72-3°. CCl3COCl (1.8 g.) added with cooling under N to 2.9 g. I, kept 2 hrs. at room temperature, and worked up gave 1.9 g. CCl3CO2Ph, b0.2 114-17°, 1.6 g. II, b0.2 128-30°, and 0.8 g. I, b0.2 178-80°, m. 71-2°. II (2.3 g.) in 10 cc. absolute Et2O added dropwise with stirring to 1.1 g. LiAlH4 in 20 cc. Et2O, refluxed briefly, and worked up yielded 1.8 g. (PhO)2CH2, b13 164-5°. II (4.7 g.) in 10 cc. dry Et2O treated with stirring at -50° with 1.8 g. dry Me2NH in a dry stream of N, kept 3 hrs. at -50°, warmed to room temperature, filtered, and distilled gave 0.9 g. (PhO)2CHNMe2, b0·.01 46-8°, and 2.8 g. I. II (2.3 g.) in 30 cc. dry Et2O treated successively with 1.0 g. C5H5N in 8 cc. dry Et2O and 1.1 g. PhSH, refrigerated 30 days, decanted, and worked up yielded 1.3 g. PhSCH(OPh)2, m. 49-50° (Et2O). p-MeOC6H4CH(OEt)2 (10.5 g.) added dropwise at -60° to 6.2 g. AcBr under dry N, warmed to 0°, diluted with 100 cc. absolute petr. ether at room temperature, cooled to -60°, and filtered gave p-MeOC6H4CHBrOEt (IV) which decompose with fuming and elimination of p-MeOC6H4CHO (phenylhydrazone m. 120.5°; semicarbazone m. 208.5°). IV (1.2 g.) and 0.6 g. PhSH in 50 cc. petr. ether treated with cooling with 0.4 g. C5H5N, kept 2 hrs. at room temperature, filtered, washed, and evaporated yielded 0.5 g. p-MeOC6H4CH(SPh)OEt, m. 80-1° (hexane). IV (2.0 g.) in 70 cc. dry petr. ether treated with stirring with 3 cc. 0.01M PhMgBr, refluxed 2 hrs., and worked up gave p-MeOC6H4CH(OEt)Ph, yellowish oil, b0.01 98-100°. AcCN (3.5 g.) added dropwise to 7.4 g. HC(OEt)3, heated 20 hrs. at 80° under N, and distilled gave 0.8 g. HCO2Et, b. 52-7°, n20D 1.3587, 3.6 g. EtOAc, b. 74-5°, n20D 1.3713, and 3.3 g. III, b12 56-8°, n25D 1.3934. PhC(OEt)3 (11.2 g.) and 3.5 g. AcCN heated 50 hrs. at 90° in a sealed tube gave 2.9 g. EtOAc, 0.8 g. AcOC(CN)2Me (V), b15 94-104°, and 4.6 g. (EtO)2C(CN)Ph, b15 126-30°, n20D 1.4815. C(OEt)4 (9.6 g.) and 3.5 g. AcCN heated 48 hrs. at 80-90° gave 3.6 g. EtOAc, some unchanged C(OEt)4, b13 46-8°, n20D 1.3940, and 3.2 g. (EtO)3CCN, b13 58-60°, n20D 1.3995. MeCH(OEt)2 (5.9 g.) and 3.5 g. AcCN heated 16 hrs. at 90° gave 1.4 g. EtOAc, unchanged AcCN, 0.5 g. MeCH(OEt)CN, b10 30-1°, n20D 1.3875, and 1.4 g. V, b11 101-2°, m. 67-8°.

Chemische Berichte published new progress about Esters. 6136-93-2 belongs to class nitriles-buliding-blocks, and the molecular formula is C6H11NO2, Name: 2,2-Diethoxyacetonitrile.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Dmitriev, Viktor; Vedekhina, Tatiana; Sapegin, Alexander; Krasavin, Mikhail published the artcile< Convenient Assembly of Privileged (Hetero)Arene-Fused Benzo[1.4]oxazepines via Two Tandem SNAr Events. Part 3 - (Hetero)arene-Fused benzo[f]imidazo[1,2-d][1,4]oxazepines>, Application of C7H3ClFN, the main research area is heteroarene fused benzo imidazo oxazepine preparation regioselective; aryl imidazole ortho dihalo halonitro arene Smiles rearrangement.

A tandem approach to (hetero)arene-fused benzo[f]imidazo[1,2-d][1,4]oxazepines I (R1 = H, Cl; R2 = H, R1 = R2 = -C4H4-; R3 = H, Me, R2 = R3 = -C4H4-; R4 = CN, NO2, COOMe, etc.; X = C, N, C-CN; Y = C, N) has been described which involves condensation of bis-nucleophilic 2-(2-hydroaryl)imidazoles II with reactivity-matched o-dihalo and o-halonitro (hetero)aromatic substrates III (LG1 = F, Cl; LG2 = F, Cl, Br, NO2). The process is generally regioselective with respect to the unsym. substituted imidazole ring and proceeds via two SNAr events (intermol. first and then intramol.) intermitted by a Smiles rearrangement. In some cases, the last SNAr step provides a rare example of nucleophilic displacement of a nitro group or a halogen in non-activated positions of a (hetero)aromatic ring which does not require the use of a metal catalyst.

ChemistrySelect published new progress about Aromatic nitro compounds Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 94087-40-8 belongs to class nitriles-buliding-blocks, and the molecular formula is C7H3ClFN, Application of C7H3ClFN.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Liu, Hao; Sun, Zhenliang; Xu, Kai; Zheng, Yan; Liu, Delong; Zhang, Wanbin published the artcile< Pd-Catalyzed Asymmetric Allylic Substitution Cascade of But-2-ene-1,4-diyl Dimethyl Dicarbonate for the Synthesis of Chiral 2,3-Dihydrofurans>, Computed Properties of 21667-62-9 , the main research area is dihydrofuran preparation asym allylic substitution cascade butene dicarbonate cyanoketone.

Herein an efficient Pd-catalyzed asym. allylic substitution cascade of both (E)- and (Z)-but-2-ene-1,4-diyl di-Me dicarbonates with α-substituted cyano ketones is described for the preparation of chiral 2,3-dihydrofurans in up to 97% yield with 98% ee. A suggested steric control process has been proposed to illustrate the differences in enantioselectivity between the reactions of (E)- and (Z)-allyl substrates. The cascade reaction could be conducted on a gram-scale, and the resulting product allows for several transformations.

Organic Letters published new progress about Alkenes Role: RCT (Reactant), RACT (Reactant or Reagent) (dicarbonates). 21667-62-9 belongs to class nitriles-buliding-blocks, and the molecular formula is C9H6ClNO, Computed Properties of 21667-62-9 .

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Whyte, Andrew; Burton, Katherine I.; Zhang, Jingli; Lautens, Mark published the artcile< Enantioselective Intramolecular Copper-Catalyzed Borylacylation>, Quality Control of 94087-40-8, the main research area is enantioselective intramol copper catalyst borylacylation; mol structure crystal boronic ester preparation chiral; asymmetric catalysis; boron; copper; cyclizations; heterocycles.

An enantioselective copper-catalyzed intramol. borylacylation is reported. The reaction proceeds through an initial enantioselective borylcupration of the styrene, followed by a nucleophilic attack on the tethered carbamoyl chloride. The products, chiral borylated 3,3-disubstituted oxindoles, were generated in excellent yields and enantioselectivities. The versatile carbon-boron bond provides a platform for a wide array of diversification.

Angewandte Chemie, International Edition published new progress about Acylation, stereoselective. 94087-40-8 belongs to class nitriles-buliding-blocks, and the molecular formula is C7H3ClFN, Quality Control of 94087-40-8.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Zhang, Ya-Kai; Wang, Bin published the artcile< Synthesis of α-Ketoamides from β-Ketonitriles and Primary Amines: A Catalyst-Free Oxidative Decyanation-Amidation Reaction>, SDS of cas: 21667-62-9, the main research area is ketoamide preparation; ketonitrile amine decyanation amidation.

AN oxidative decyanation-amidation of β-ketonitriles and primary amines readily occurs using hydrogen peroxide sodium carbonate adduct (Na2CO3·1.5H2O2), K2CO3, and 1,4-dioxane. This reaction affords α-ketoamides under mild conditions without the need of a catalyst.

European Journal of Organic Chemistry published new progress about Amidation. 21667-62-9 belongs to class nitriles-buliding-blocks, and the molecular formula is C9H6ClNO, SDS of cas: 21667-62-9.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts