Fluorophenyl derivatives of elements II-VI groups

The enthalpies and temperatures of melting of RSi(CH₃)₃, R₄Si, R₃P, R₃As, R₃Sb, R₃Bi, R₂Te and R₂Hg (R=C₆F₅) were obtained by scanning calorimetry measurements. The pressure of the saturated and unsaturated vapors of RSi(CH₃)₃, R₂Si(CH₃)₂, R₄Si, R₃Ga, R₃P, R₃As, R₃Sb, R₃Bi, R₂Te and R₂Hg has been measured by the static method with a membrane-gauge manometer. It was established that all investigated substances proceeded to vapor as monomers. Equations approximating the dependences of saturated vapor pressures on temperature and the enthalpies and entropies of vaporization were obtained. Grafite films with silicon intercalated up to 25 at.% were grown by CVD using R₄Si as a precursor. These films showed semiconductor properties in the temperature interval 80–300 K.     

An unexpected highly diastereoselective double Baylis-Hillman reaction of per- (or poly)fluorophenyl aromatic aldimines with methyl vinyl ketone

Aza-Baylis-Hillman reaction of per- (or poly)fluorophenyl aromatic aldimines 1 with methyl vinyl ketone (MVK) was studied. It was found that both the used Lewis base and solvent can significantly affect the reaction. Using triphenylphosphine as a Lewis base, the reaction of 1 with MVK proceeded smoothly to give the normal Baylis-Hillman adduct 2 along with the double Baylis-Hillman adduct 3 as by-product in THF. When 1,4-diazabicyclo[2.2.2]octane was used as a Lewis base in DMF, the aza-Baylis-Hillman reaction of 1 with MVK gave the double aza-Baylis-Hillman adduct 3 exclusively in moderate to good yields with excellent diastereoselectivities. The double Baylis-Hillman adduct 3 was conveniently converted to fluorine-containing 4-alkylidene-2-cyclohexen-1-ones under mild reaction conditions in good yields.     

Synthesis of α‐(Fluorophenyl)pyridine by Palladium‐Catalyzed Cross‐Coupling Reaction

A series of α‐(fluoro‐substituted phenyl)pyridines have been synthesized by means of a palladium‐catalyzed cross‐coupling reaction between fluoro‐substituted phenylboronic acid and 2‐bromopyridine or its derivatives. The reactivities of the phenylboronic acids containing di‐ and tri‐fluoro substituents with α‐pyridyl bromide were investigated in different catalyst systems. Unsuccessful results were observed in the Pd/C and PPh₃ catalyst system due to phenylboronic acid containing electron‐withdrawing F atom(s). For the catalyst system of Pd(OAc)₂/PPh₃, the reactions gave moderate yields of 55% –80%, meanwhile, affording 10% –20% of dimerisation (self‐coupling) by‐products, but trace products were obtained in coupling with 2,4‐difluorophenylboronic acids because of steric hinderance. Pd(PPh₃)₄ was more reactive for boronic acids with sterically hindering F atom(s), and the coupling reactions gave good yields of 90% and 91% without any self‐coupling by‐product.     

(4R-cis)-6-[2-[2-(4-氟苯基)-5-(1-异丙基)-3-苯基-4-[苯胺(羰基)]-1 H-吡咯-1-基]乙基]-2,2-二甲基-1,3-二氧己环-4-乙酸叔丁酯的波谱学研究

对(4R-cis)-6-[2-[2-(4-氟苯基)-5-(1-异丙基)-3-苯基-4-[苯胺(羰基)]-^1H-吡咯-1-基]乙基]-2,2-二甲基-1,3-二氧己环-4-乙酸叔丁酯的傅里叶变换离子回旋共振质谱(FT-ICR-MS)、核磁共振氢谱(^1H-NMR)、碳谱(^13C-NMR)以及^1H同核位移相关谱(^1H-^1HCOSY)、检出^1H的异核多量子相干谱(HMQC)和^1H检测的异核多键相关谱(HMBC)报道并进行解析。确定了^1H谱、^13C谱中各谱峰的归属,研究了其六元环部分的立体构象,并就空间效应对其化学位移的影响做了初步的探讨。     

Synthesis of 10‐Aryl‐ and 10‐(Arylmethyl)acridin‐9(10H)‐ones via the Reaction of (2‐Fluorophenyl)(2‐halophenyl)methanones with Benzenamines and Arylmethanamines

The reaction of 1‐fluoro‐2‐lithiobenzenes, generated from 1‐bromo‐2‐fluorobenzenes 1 and BuLi, with 2‐halobenzaldehydes and subsequent oxidation of the resulting alcohols 2 afforded (2‐fluorophenyl)(2‐halophenyl)methanones 3 , which, on treatment with benzenamines or arylmethanamines, followed by NaH, gave rise efficiently to 10‐aryl‐ or 10‐(arylmethyl)acridin‐9(10H)‐ones ( 5 or 7 ), respectively.     

Microwave‐Assisted Synthesis of 10‐(Phthalimidoalkyl)‐halosubstitutedpyrido [3,2‐b][1,4]‐benzothiazine in Dry Media

N‐Alkylation of 10H‐9‐fluoropyrido[3,2‐b][1,4]‐benzothiazine 5a, 10H‐7‐fluoropyrido[3,2‐b][1,4]‐benzothiazine 5b, and 10H‐7‐chloropyrido[3,2‐b][1,4]‐benzothiazine 5c with different N‐(bromoalkyl)phthalimides using anhydrous K₂CO₃ and tetrabutylammonium bromide (TBAB) under dry conditions with microwave irradiation leads to the formation of 10‐(phthalimidoalkyl)‐halosubstitutedpyrido[3,2‐b][1,4]‐benzothiazine (6a–f) along with some unidentified product. Compound 5a is a new azaphenothiazine derivative and was obtained from hitherto unknown 2‐acetylamino‐3‐fluorophenyl‐3′‐nitro‐2′‐pyridylsulfide 4a via Smiles rearrangement. Compound 4a is required for the synthesis and has been prepared starting from 2‐amino‐3‐fluorobenzenethiol 1a in three steps.     

Synthesis and Bioactivity of Novel N,N′‐Diacylhydrazine Derivatives Containing Furan(I)

The furan ring system possesses electron‐rich properties and exhibits various biological activities, which was introduced into diacylhydrazine to create novel leading compounds that may serve as improved pesticides and pharmaceuticals. A series of novel diacylhydrazine derivatives containing a furan ring were synthesized by the reaction of 5‐fluorophenyl‐2‐furoyl chloride with substituted benzoylhydrazide in anhydrous dichloromethane under reflux. The structures of the resultant compounds were confirmed by IR, ¹H NMR, MS and elemental analysis. Insecticidal and anti‐tumor activities of these new compounds were evaluated.     

N-取代芳酰氨基-5-氟代苯基-2-呋喃甲酰硫脲的合成与生物活性测定

从5-氟代苯基-2-呋喃甲酸出发, 经酰化、异硫氰酸酯化, 再与取代芳酰肼反应合成了20个未见文献报道的N-取代芳酰氨基-5-氟代苯基-2-呋喃甲酰硫脲. 目标产物的结构经IR, ¹H NMR和元素分析测定确证. 初步生物活性测试表明, 部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性; 部分目标化合物有较好的除草活性.     

Organomercury Compounds. 32. Syntheses of Fluorophenylmercurials by Decarboxylation

The organomercury compounds HgR₂ (R = 2-Cl,6-FC₆H₃, 2,6-F₂C₆H₃, 2,3,6-F₃C₆H₂, m-HC₆F₄, p-HC₆F₄, or C₆F₅) and RHg(O₂CR) (R = 2-Cl,6-C₆H₃, 2,6-F₂C₆H₃ or 2,3,6-F₃C₆H₂) have been obtained in moderate – good and low yields respectively from decarboxylation reactions of the corresponding mercury(II) fluorobenzoates in boiling pyridine. By contrast, mercury(II) 2,3,4-5-tetrafluorobenzoate gave a low yield of CO₂, a trace of Hg(o-HC₆F₄)₂ and a very low yield of o-HC₆F₄Hg(O₂CC₆F₄H-o). The ¹⁹⁹Hg NMR spectra of the diorganomercurials (R = 2-Cl,6-FC₆H₃, 2,6-F₂C₆H₃, 2,3,6-F₃C₆H₂, 2,4,6-F₃C₆H₂, 2,6-Cl₂C₆H₃, o-HC₆F₄, m-HC₆F₄, p-HC₆F₄ or C₆F₅) are discussed.