Synthesis of 1,3,3,5,5-Penta[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]-1-[(1H-1,2,3-triazol-4-yl)alkoxy]cyclotriphosphazenes

Russian Journal of General Chemistry - Based on 1,3,3,5,5-penta[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]-1-chlorocyclotriphosphazene, a series of hybrid compounds was obtained by two-step...     

New liquid crystal compounds ( )-4-[5-(2-Methylbutyl)-1,3-dioxan-2-yl]phenyl 4-alkoxybenzoate

New liquid crystal compounds, (+)-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl] phenyl 4-alkoxybenzoates (5), were synthesized. The mesomorphic behaviour of these compounds is compared with that of (+)-4-(5-alkyl-1,3-dioxan-2-yl)-phenyl 4-(2-methylbutoxy)benzoates (6). While compounds 6 exhibited a chiral smectic C phase, the corresponding compounds 5 did not. This might mean that for the appearance of a chiral smectic C phase in these types of compounds, it is necessary that the carbonyl and the chiral groups exist at nearby positions. Transition temperatures to those isotropic state for compounds 5 were lower than those for compounds 6. This result is common in both cases of (+)-4-alkoxycarbonylphenyl-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl]benzoates (7), and (+)-4-(2-methylbutoxy-carbonyl)phenyl 4-(5-alkyl-1,3-dioxan-2-yl)-benzoates (8).     

Synthesis of 5-[bromo(aryl)methyl]-2,2-dimethyl-1,3-oxazolidin-4-ones

A Darzens condensation of α-chloroacetamide with aromatic aldehydes furnished a series of 3-aryl-2,3-epoxypropionamides, which were further converted to 5-[bromo(aryl)methyl]-2,2-dimethyl-1,3-oxazolidin-2-ones.     

N,N′-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺在空气中的热分解动力学研究

以TG-DTG为手段, 研究了N,N′-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺(DPTDEDA)在空气中的热分解动力学,利用Friedman法、Flynn-Wall-Ozawa(FWO)法对DPTDEDA进行了动力学分析, 求出了该物质两个主要的热分解阶段的热分解动力学参数, 同时利用Coats-Redfern法、Achar法研究了该物质的热分解机理. 结果表明, 用Friedman法所求得的两个热分解阶段的表观活化能的平均值分别为128.03和92.59 kJ•mol^－1; 而Flynn-Wall-Ozawa法所求得的两个热分解阶段的表观活化能的平均值分别为138.75和106.78 kJ•mol^－1. 由Coats-Redfern法、Achar法得出DPTDEDA在空气中的热分解过程虽主要分为两段反应, 但经过推理其反应机理函数却是相同的, 为f(α)＝3/2(1－α)^4/3[(1－α)^－1/3－1]^－1.     

新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基- 2-氧)苯的合成及热分解动力学研究

以新戊二醇、三氯氧磷及1,3,5-三羟基苯等为原料, 经过两步反应合成新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基-2-氧)苯, 采用元素分析、FT-IR、MS及1H NMR等技术确定了标题化合物的分子结构. 以TG-DTG为手段, 研究该新型磷系阻燃剂在氮气气氛中的热分解动力学; 利用Kissinger法、Flynn-Wall-Ozawa (FWO)法对其进行热分解动力学研究, 求出该阻燃剂的热分解动力学参数; 利用Coast-Redfern法研究该阻燃剂的热分解机理. 结果表明, Kissinger法所求得的表观活化能为171.72 kJ•mol－1, 指前因子ln A为37.57; Flynn-Wall-Ozawa法所求得的表观活化能为172.05 kJ•mol－1. 标题化合物的热分解动力学方程g(α)＝α1/4, 反应级数n＝1/4.     

Synthesis, spectroscopic and DFT investigation of dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate

Dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate has been synthesized and characterized by elemental analysis, FT-IR and ¹H, ¹³C and ³¹P NMR. The vibrational wavenumbers, gauge including atomic orbital (GIAO) ¹H and ¹³C chemical shift values of title compound in the ground state have been computed with density functional theory method (DFT) and the B3LYP functional. The basis sets used are 6-311G(d,p) and 6-31G(d). The harmonic vibrational wavenumbers have been computed and the scaled values have been compared with the experimental FT-IR spectra. The complete assignments have been performed on basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Most of the computed wavenumbers are found to be in good agreement with the observed spectrum.     

无溶剂、无催化剂条件下5-[(3-吲哚基)-芳甲基]-2,2-二甲基- 1,3-二氧六环-4,6-二酮的合成

在无溶剂和催化剂条件下,由芳香醛、吲哚、丙二酸亚异丙酯的三组分缩合反应,制备了5-[(3-吲哚基)-芳甲基]-2,2-二甲基-1,3-二氧六环-4,6-二酮,产率为70%～85%,产物结构经1H NMR,IR确证.     

Study on thermal decomposition kinetics of N,N′-bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine in air

The thermal decomposition kinetics of the N,N′-bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) ethylenediamine (DPTDEDA) in air were studied by TGDTG techniques. The kinetic parameters of the decomposition process for the title compound in the two main thermal decomposition steps were calculated through the Friedman and Flynn-Wall-Ozawsa (FWO) methods and the thermal decomposition mechanism of DPTDEDA was also studied with the Coats-Redfern and Achar methods. The results show that the activation energies for the two main thermal decomposition steps are 128.03 and 92.59 kJ·mol⁻¹ with the Friedman method, and 138.75 and 106.78 kJ·mol⁻¹ with the FWO method, respectively. Although there are two main thermal decomposition steps for DPTDEDA in air, the thermal decomposition mechanism of DPTDEDA in the two steps are the same, i.e. f(α) = 3/2(1 − α)^4/3[(1 − α)^−1/3 − 1]⁻¹. __________ Translated from Acta Chimica Sinica, 2008, 66(9) (in Chinese)     

Synthesis of 3-(2-(4,5-Dihydro-3,5-diphenylpyrazol-1-yl)thiazol-4-yl)-2H-chromen-2-one Derivatives via Multicomponent Approach

An efficient synthesis of 3-(2-(4,5-dihydro-3,5-diphenylpyrazol-1-yl)thiazol-4-yl)-2H-chromen-2-one derivatives by a simple, atom-economical, and multicomponent reaction of chalcones, thiosemicarbazide, and 3-(2-bromoacetyl) coumarins in the presence of aqueous sodium hydroxide in refluxing ethanol is reported. The structures of newly prepared compounds have been confirmed by their analytical and spectral (IR, ¹HNMR, ¹³CNMR and mass) data.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

N,N'-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺的热分解动力学研究

以TG-DTG为手段, 研究了N,N'-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺(DPTDEDA)在氮气气氛中的热分解动力学, 利用 Kissinger法、Flynn-Wall-Ozawa(FWO)法对DPTDEDA进行了动力学分析, 求出了该物质的热分解动力学参数, 同时利用Satava-Sestak法研究了该物质的热分解机理. 结果表明, Kissinger法所求得的表观活化能为137.37 kJ•mol^－1, 指前因子ln A＝28.00; Flynn-Wall-Ozawa法所求得的活化能为139.83 kJ•mol^－1. DPTDEDA的热分解机理为相边界反应, 其动力学方程为G(α)＝1－(1－α)⁴, 反应级数n＝4.     

N-苄基-3(S)-邻苯二甲酰亚胺基-4(S)-[4(S)-2,2-二甲基-1,3-二氧环戊-4-基]-2-氧吖丁啶的合成

以L-抗坏血酸(1)为原料,经3步反应制得(S)-缩异丙氧叉甘油醛(4).该手性醛与苄胺缩合制得相应的手性亚胺(5).甘氨酸经保护后制成酰氯,在有机碱作用下首先生成不稳定的烯酮(8),继与手性亚胺5迅速进行[2+2]环加成反应,合成标题化合物N-苄基-3(S)-邻苯二甲酰亚胺基-4(S)-[4(S)-2,2-二甲基-1,3-二氧环戊-4-基]-2-氧吖丁啶.由于环加成的面向立体选择性容易控制,由此所得产物的光学纯度和化学收率均较高     

Synthesis and Properties of Alkyl 2-[2-(Diarylmethylidene)hydrazinyl]-5,5-dimethyl-4-oxohex-2-enoates

Russian Journal of Organic Chemistry - Ring opening of 3-[(diarylmethylidene)hydrazinylidene]-5-tert-butylfuran-2(3H)-ones by the action of alcohols afforded previously unknown alkyl...     

Synthesis of Substituted 6-Amino-4-aryl-5-cyano-2H,4H-pyrano[2,3-c]pyrazoles. Crystal and Molecular Structure of 6-Amino-5-cyano-3-methyl-4-(2',4',6'-triethylphenyl)-2H,4H-pyrano[2,3-c]pyrazole

Substituted 6-aminopyrano[2,3-c]pyrazoles were synthesized by the two-component condensation of arylidenemalononitriles and substituted 5-pyrazolones or three-component condensation of aromatic aldehydes, malononitrile, and substituted 5-pyrazolones. It was established by X-ray crystallographic analysis that pyranopyrazoles exist in the 2H and not the 1H tautomeric form.     

5-[5-R-furfurylidene]-2,2-dimethyl-1,3-dioxane-4,6-diones 6. Synthesis,structure, and properties of substituted furylimino- and furfurylidenephosphoranes. Molecular and crystal structure of N-[5-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)methyl-2-furylimino(triphenyl)phosphorane

Furylimino- and furfurylidenephosphoranes have been synthesized by sequential conversions of 5-unsubstituted and 5-methylfurfut),Iidetiedio.yanediones. The ylide fragment linked directly with the furfurylidenedioxanedione residue displays strong electron-donating properties, as a result of which resonance occurs in the system of conjugated bonds. The molecular and crystal structure of the iminophosphorane was studied by x-ray structural analysis and the resonance of the bonds in the molecule was confirmed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 335–344, March, 1994.     

新型1-(1,3,5-三嗪-6-基)-3-甲基-4-(5-苯基-1,3,4-噁二唑-2-基)吡唑的合成及活性评价

设计合成了18个以吡唑桥连1,3,4-噁二唑和1,3,5-三嗪的新型多杂环分子[7A(a~f),7B(a~f)和7C(a~f)];通过红外光谱(IR)、核磁共振波谱(NMR)和高分辨质谱(HRMS)等对目标分子进行了结构表征;评价了目标分子对蛋白酪氨酸磷酸酯酶1B(PTP1B)和细胞分裂周期25磷酸酯酶B(Cdc25B)的抑制活性.结果表明,所有目标分子对PTP1B和Cdc25B均有较好的抑制活性,其中,9个目标分子表现出优异的PTP1B和Cdc25B抑制效果,IC50值低于齐墩果酸(PTP1B抑制活性测试参照物)和正钒酸钠(Cdc25B抑制活性测试阳性参照物),有望成为潜在的PTP1B和Cdc25B抑制剂.     

Synthesis of New {2-[3(4)-Nitrophenyl]-5-chloromethyl-1,3-dioxan-5-yl}methyl-4-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) Benzoates

Russian Journal of General Chemistry - The reaction of 2-[3(4)-nitrophenyl]-5,5-dichloromethyl-1,3-dioxanes with potassium 4-aminobenzoate in dimethylformamide gave...     

Synthesis, Crystal Structure and Thermal Properties of N,N′-Bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) Ethylene Diamine

The title compound N,N′-bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) ethylene diamine (DPTDEDA, C12H26N2O4P2S2) was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and 1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557(16), b = 11.299(12), c = 12.163(13) , β = 98.707(19)°, Dc = 1.305 g/cm3, Z = 4, λ = 0.71073 , μ(MoKα) = 0.447 mm-1, Mr = 388.41, V = 1977(4) 3, F(000) = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections (I > 2σ(I)). X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N–H···S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.     

Synthesis of 3-[4-(1-Benzofuran-2-yl)-1,3-thiazol-2-yl]-2-(4-aryl)-1,3-thiazolidin-4-one Derivatives as Biological Agents

A protocol for the synthesis of 3-[4-(1-benzofuran-2-yl)-1,3-thiazol-2-yl]-2-(4-aryl)-1,3-thiazolidin-4-one derivatives (5a–e) has been developed from 1-(1-benzofuran-2-yl)-2-bromoethanone (2),which served as a key intermediate for the synthesis of the title compounds. The reaction of compound 2 with thiourea furnished 4-(1-benzofuran-2-yl)-1,3-thiazol-2-amine 3, which upon further reaction with various aromatic aldehydes, gave Schiff bases 4a–e. These Schiff bases, when treated with thioacetic acid in the presence of catalytic amount of anhydrous ZnCl₂, yielded thiazolidinone derivatives 5a–e. All the newly synthesized compounds have been characterized by analytical and spectral data and screened for their antimicrobial and analgesic activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.