A New Route to Phosphoryl Thiocarbonyl Mixed Imides - Structure Limitations

Abstract

The rearrangement of N-methyl thiophosphoryl carbonyl mixed imides (I, XYP(S)N(Me)C(O)Z) to N-methyl phosphoryl thiocarbonyl mixed imides (II, XYP(O)N(Me)C(S)Z) was studied as a function of substitution on phosphorus (Ia: X = Y = MeO; Ib: X = Ph, Y = MeO; and Ic: X = Y = Ph) with Z = Ph and as a function of substitution on carbon (Ia: Z = Ph; Id: Z = Me; and Ie: Z = OiBu) with X = Y = MeO. For Ia, Ib, and Id, rearrangement is complete and quantitative. In contrast, Ic rearranges to a 10/90 equilibrium mixture of IIc/Ic and Ie gives no evidence for rearrangement to the phosphoryl thiocarbonyl mixed imide IIe. A relative reactivity order for Ia, Ib, Ic, and Id of 1.00, 0.15, 0.036, and 0.11 respectively, was observed in the rearrangements.     

Marine natural products. XXVI. Biologically active tridecapeptide lactones from the Okinawan marine sponge Theonella swinhoei (Theonellidae). (2). Structures of theonellapeptolides Ia, Ib, Ic, and Ie

Five tridecapeptide lactones, named theonellapeptolides Ia (1), Ib (2), Ic (3), Id (4), and Ie (5), were isolated from the Okinawan marine sponge Theonella swinhoei. Following the structure elucidation of theonellapeptolide Id (4), the structures of theonellapeptolides Ia (1), Ib (2), Ic (3), and Ie (5) were determined on the basis of chemical and physicochemical evidence including high performance liquid chromatography and circular dichroism combined analysis of the amino acid compositions. Theonellapeptolides Ib (2), Ic (3), Id (4), and Ie (5) exhibit moderate cytotoxic activity towards for L1210 in vitro (IC50 1.6, 1.3, 2.4, and 1.4 micrograms/ml, respectively), and theonellapeptolide Ie (5) exhibits ion-transport activities for Na+ and K+ ions.     

Polymerizations of substituted cyclopropanes. I. Radical polymerization of 1,1-disubstituted 2-vinylcyclopropanes

Diethyl 2-vinylcyclopropane-1,1-dicarboxylate (Ia), 2-vinylcyclopropane-1,1-dicarbonitrile (Ib), ethyl 1-cyano-2-vinylcyclopropanecarboxylate (Ic), and 1,1-diphenyl-2-vinylcyclopropane (Id) were radically homo- and copolymerized. Ia, Ib, and Ic polymerized cleanly in 1,5-type ring-opening fashion to yield polymers of high molecular weight. Id failed to homopolymerize but copolymerized with common monomers which included maleic anhydride. Infrared (IR) spectra indicated that the double bonds of the polymer chains were in trans form. All polymers were soluble in solvents and solution-cast films were clear and flexible, showing T_g values in the 25–40°C range. Model reactions of those monomers with benzenethiol also indicated predominant 1,5-addition reactions. From the results of our investigation it was concluded that the driving force for the facile radical 1,5-polymerization of Ia, Ib, and Ic was the stabilization of growing radicals by two substituents.     

Mass spectral studies of some aryl and aroyl derivatives of glyoxime

Mass spectra of two diaroylglyoximes (Ia and Ib) are reported and compared with those of the corresponding dehydration products, 3,4-diaroyl-1,2,5-oxadiazoles (IIIa and IIIb, respectively). In Ia and Ib, unlike in diarylglyoximes (Id and Ie), the largest ion is [M — 18]⁺, but this does not form in the ion source by a simple thermal dehydration. Similar spectra have been obtained for an alkyl aroyl derivative of glyoxime (Ic) and an isonitroso-β-diketone (II). A specific electron-impact-induced rearrangement leading to the formation of carboxylic acids has been observed in the mass spectra of all the acylated oximes under investigation.     

Polymerization systems driven by aromatization energy: Anionic polymerization of 4-allylidene-2,6-dimethyl-2,5-cyclohexadien-1-one and spiro[2,5]octadienone derivatives

To investigate the polymerization systems driven by aromatization energy, 4-allylidene-2,6-dimethyl-2,5-cyclohexadien-1-one ( Ia ), 5,7-dimethyl-1-vinylspiro[2,5]octa-4,7-dien-6-one ( Ib ), 4,7-dimethyl-1-vinylspiro[2,5]octa-4,7-dien-6-one [ Ic ], 2-vinyl-2′-methylspiro[cyclopropane-1,4′-(1′-naphthalenone)] ( Id ), and 2-phenyl-2′-methylspiro[cyclopropane-1,4′-(1′-naphthalenone)] ( Ie ) were prepared and polymerized with sodium cyanide in N,N-dimethylformamide. Monomer Ia was highly polymerizable even at ?65°C. Monomers Ib–Ie also polymerized well, giving powdery polymers that were soluble in common solvents. All the polymerizations took place through the aromatization of the cyclohexadienone ring, suggesting that the aromatization energy is the driving force for the polymerization of these monomers.     

Surface-active properties of new cationic gemini surfactants with cyclic spacer

Three cationic gemini surface active compounds of the type (1r,4r)-1,4-dialkyl-1,4-dimethy-l-piperazine-1,4-diium bromide (Ia, Ib, and Ic), were synthesized. They were characterized using elemental analysis and ¹H-NMR spectra. Their surface-active properties were measured in aqueous solutions with different concentrations at different temperatures (25, 40, and 55°C). Various surface measurements of these gemini surfactants, (compared to the conventional one, 1-Dodecyl-1-methylpiperidinium bromide (a)) were estimated, specifically critical micelle concentration (CMC), effectiveness (π_CMC), efficiency (P_C20) as well as maximum surface excess (Γ_max) and minimum surface area (A_min). The measurements of the gemini compounds gave low CMC, high efficiency in reducing the surface tension, and intense adsorption at air/water interface. These surfactants have lower Krafft points and thus better solubility. Thermodynamic data, free energy, entropy, and enthalpy changes (ΔG°, ΔS°, and ΔH°) for micellization at the air/water interface and also for adsorption in the bulk of surface-active solutions were calculated.     

Synthesis and properties of nonylphenol-substituted dodecyl sulfonate

Nonylphenol-substituted dodecyl sulfonate (C₁₂-NPAS) was synthesized via sulfonation-alkylation-neutralization using 1-dodecene, SO₃, and nonylphenol as raw materials. The properties such as surface tension, interfacial tension (IFT), wettability, foam properties, and salinity tolerance of C₁₂-NPAS were systematically investigated. The results show that the critical micelle concentration (CMC) of C₁₂-NPAS was 0.22?mmol?·?L^?1 and the surface tension at the CMC (γ_CMC) of C₁₂-NPAS was 29.4 mN/m. When compared with the traditional surfactants sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl sulfate (SDS), and linear alkylbenzene sulfonate (LAS), the surface properties of C₁₂-NPAS were found to be superior. The IFT between Daqing crude oil and a weak-base alkaline/surfactant/polymer (ASP) oil flooding system containing 0.1?wt% of C₁₂-NPAS can reach an ultralow level of 2.79?×?10^?3 mN/m, which was lower than that found for the traditional surfactant heavy alkylbenzene sulfonate (HABS). The salinity and hardness tolerance of C₁₂-NPAS were much stronger than those found for conventional surfactants, petroleum sulfonate, and LAS. C₁₂-NPAS also shows improved wetting performance, foamability, and foam stability.     

Surface activity and thermodynamic properties of water‐soluble polyester surfactants based on 1,3‐dicarboxymethoxybenzene used for enhanced oil recovery

The surface activity and thermodynamic properties for eight low molecular weight nonionic co‐polyester (PE) surfactants have been investigated. Surface and interfacial tensions (IFT) of surfactants in aqueous solutions were measured using the spinning drop technique. From these measurements, the critical micelle concentration (CMC), the surface pressure at CMC (Y_CMC), the maximum surface concentration (Γ_max), the minimum area/molecule at the aqueous solution/air interface (A_min), the effectiveness of surface tension reduction (Π_CMC), the alkane carbon number (n_min) and the IFT at n_min (Y_min) were determined. The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic and ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad and ΔS_ad) for these polymeric surfactants were also calculated. Structural effects on micellization and adsorption are discussed in terms of these parameters. The results show that the ΔG_ad values were more negative than ΔG_mic values for these compounds, so that they favored adsorption before the micellization process. They exhibited IFT in the order of 10⁻³ to 10⁻⁴ mN/m against the thin alkane carbon number range 6–9. This range seemed to be prefered for enhanced oil recovery. Copyright © 2000 John Wiley & Sons, Ltd.     

Polymerizations of substituted cyclopropanes. II. Anionic polymerization of 1,1-disubstituted 2-vinylcyclopropanes

Among the four 1,1-disubstituted 2-vinylcyclopropanes, diethyl 2-vinylcyclopropane-1,1-dicarboxylate (Ia), 2-vinylcyclopropane-1,1-dicarbonitrile (Ib), ethyl 1-cyano-2-vinylcyclopropanecarboxylate (Ic), and 1,1-diphenyl-2-vinylcyclopropane (Id), Ib and Ic polymerized well with sodium cyanide in N,N-dimethylformamide. Ib was most reactive and a polymer (IIb) from Ib exhibited an inherent viscosity of 1.05 dl/g (concentration of 1.0 g in 100 ml of 95% H₂SO₄). All experimental results indicated that the polymerization proceeded by ring opening and that the structure of the polymers had pendant vinyl groups. The polymer IIc from Ic was soluble in common solvents like acetone, but IIb was soluble only in 95% H₂SO₄. Reactions of those compounds with benzenethiolate ion in ethanol yielded addition products that supported the ring-opening polymerization of those monomers. In the postulated mechanism of polymerization cyanide ion attacks the carbon of a cyclopropane ring with electron-releasing vinyl group and the resulting anion is thereby stabilized by two electron-withdrawing substituents. The propagation takes place by the reaction of the anion with another monomer molecule.     

CMC系列高分子表面活性剂与原油超低界面张力形成机理的研究

采用动态激光光散射及环境扫描电镜研究了羧甲基纤维素系列高分子表面活性剂与大庆原油形成超低界面张力的机理.结果表明,CMC系列高分子表面活性剂具有与低分子量表面活性剂相比拟的表/界面活性,其水溶液的表面张力可达2835mN/m,界面张力达到10^-110mN/m.碱的加入可显著降低高分子表面活性剂与原油的界面张力,在适当条件下界面张力达到超低值(10^-3mN/m),可望作为三次采油的驱油剂.等效烷烃模型研究表明,用碱与原油酸性组分的作用来解释碱能使界面张力下降至超低值的传统观点是不完善的,加入碱能使高分子表面活性剂胶束解缔,胶束数量增多,胶束粒径减小,单分子自由链增加,有利于高分子表面活性剂向界面迁移和排布,这是高分子表面活性剂和碱复配体系与原油界面张力下降至超低值的主要原因.     

Aggregation behavior of silicone surfactants in ethylammonium nitrate ionic liquid

The aggregation behavior of two silicone surfactants (monomeric and Gemini) was studied by surface tension measurements in a room temperature ionic liquid, ethylammonium nitrate (EAN), at various temperatures. A series of parameters, including critical micelle concentration (CMC), surface tension at the CMC (γ _CMC), adsorption efficiency (pC ₂₀), and effectiveness of surface tension reduction (Π _CMC), were obtained. By comparing the silicone surfactants with traditional surfactants, we deduced that the surface activity of the silicone surfactants in EAN was superior to the activity of other surfactants. In addition, from the CMC values and their temperature dependence, we estimated the thermodynamic parameters of the micelle formation, $ \Delta G_m^0 $ , $ \Delta H_m^0 $ , and $ \Delta S_m^0 $ . It was revealed that the micellization of the silicone surfactants is entropy driven at low temperature and enthalpy driven at high temperature. Isothermal titration calorimetry measurements were also carried out to study the micellization of Gemini silicone surfactant. ¹H NMR was performed to study the silicone surfactant micelle formation mechanism in EAN.     

Two novel polymorphic forms of iron‐chelating agent deferiprone

Thalassemia is a genetic blood disorder requiring life‐long blood transfusions. This process often results in iron overload and can be treated by an iron‐chelating agent, like deferiprone (3‐hydroxy‐1,2‐dimethylpyridin‐4‐one), C₇H₉NO₂, in an oral formulation. The first crystal structure of deferiprone, (Ia), was reported in 1988 [Nelson et al. (1988). Can. J. Chem. 66 , 123–131]. In the present study, two novel polymorphic forms, (Ib) and (Ic), of deferiprone were identified concomitantly with polymorph (Ia) during the crystallization experiments. Polymorph (Ia) was redetermined at low temperature for comparison of the structural features and lattice energy values with polymorphs (Ib) and (Ic). Polymorph (Ia) crystallized in the orthorhombic space group Pbca, whereas both polymorphs (Ib) and (Ic) crystallized in the monoclinic space group P2₁/c. The asymmetric units of (Ia) and (Ib) contain one deferiprone molecule, while polymorph (Ic) has three crystallographically independent molecules (A, B and C). All three polymorphs have similar hydrogen‐bonding features, such as an R₂²(10) dimer formed by O—H…O hydrogen bonds, an R₄³(20) tetramer formed by C—H…O hydrogen bonds and π–π interactions, but the polymorphs differ in their molecular arrangements in the solid state and are classified as packing polymorphs. O—H…O and C—H…O hydrogen bonds lead to the formation of two‐dimensional hydrogen‐bonded parallel sheets which are interlinked by π–π stacking interactions. In the three‐dimensional crystal packing, the deferiprone molecules were aggregated as corrugated sheets in polymorphs (Ia) and (Ic), whereas in polymorph (Ib), they were aggregated as a square‐grid network. The characteristic crystalline peaks of polymorphs (Ia), (Ib) and (Ic) were established through powder X‐ray diffraction analysis. The Rietveld analysis was also performed to estimate the contribution of the polymorphs to the bulk material.     

Lipophilic counterion effect on aggregation and adsorption behavior of quaternary ammonium surfactants

The obvious different aggregation and adsorption behavior of six newly quaternary ammonium surfactants with different lipophilic counterions has been discoverd by measurements of equilibrium and dynamic surface tension, fluorescence and conductivity. Interestingly, the critical micelle concentration (CMC) and its surface tension γ_CMC decrease with the increasing counterion chain length. However, three methods have confirmed that an exception of CMC increases slightly from C₁₆NC₁ to C₁₆NC₂. According to experimental results, a balanced mechanism between hydrophobicity and electrostatic of counterion is proposed. Besides, the dynamic surface tension results show the diffusion coefficient increases with the increasing counterion length both at a short time (D_t?→?0) and long time (D_t?→?∞), which indicates a faster adsorption process. Unlike the inorganic counterion, the diffusion coefficient decreases with the increase of hydrophobic chain length. This is attributed to the strong electrostatic interactions between counterions and cationic headgroups.     

界面扩张流变法研究C12mimBr对Gemini12-2-12在空气/水界面聚集行为的影响

采用界面扩张流变技术研究了季铵盐偶联表面活性剂C₁₂-(CH₂)₂-C₁₂·2Br (Gemini12-2-12)及其与离子液体表面活性剂溴化1-十二烷基-3-甲基咪唑(C₁₂mimBr)复配体系的动态界面张力、扩张流变性质和界面弛豫过程等, 探讨了C₁₂mimBr 对C₁₂mimBr/Gemini12-2-12 混合体系界面性质的影响及C₁₂mimBr 对Gemini12-2-12界面聚集行为影响的机制. 结果表明, 随着离子液体表面活性剂的不断引入, 体系界面吸附达到平衡所需的时间逐渐缩短, 扩张模量和相角明显降低, 界面吸附膜由粘弹性膜转变为近似纯弹性膜; 同时, 界面及其附近的弛豫过程也发生显著变化, 慢弛豫过程消失, 快弛豫过程占主导地位, 且离子液体浓度越高, 快弛豫的贡献越大. 这些界面性质的变化主要归因于离子液体表面活性剂C₁₂mimBr参与界面形成及两表面活性剂在界面竞争吸附的结果. 少量离子液体表面活性剂C₁₂mimBr 的加入可以填补疏松的Gemini12-2-12 界面上的空位, 形成混合界面吸附膜. 随着C₁₂mimBr 含量的增加, 嵌入界面的C₁₂mimBr 分子数不断增多, 导致界面上相互缠绕的Gemini12-2-12烷基链“解缠”, 在体相和界面分子扩散交换的过程中“解缠”的Gemini12-2-12分子从界面上解吸回到体相, 与此同时, C₁₂mimBr 分子相对较小的空间位阻及较强的疏水作用促使其优先扩散至界面进而取代Gemini12-2-12分子, 最终界面几乎完全被C₁₂mimBr分子所占据.     

Ring transformation of 6-methyl-3,4-dihydro-2H-1,3-oxazine-2,4-diones

Ring transformation of 6-methyl-3,4-dihydro-2H-1,3-oxazine-2,4-dione (Ia) and its N-sub-stituted derivatives, such as 3-methyl (Ib), 3-ethyl (Ic), and 3-benzyl (Id) derivatives is described. Reaction of Ia with hydrazine hydrate gave 1-amino-6-methyluracil (II), while Id reacted with hydrazine hydrate to give 3-hydroxy-5-methylpyrazole (III). Reaction of Ia,b,d with ethyl acetoacetate in ethanol in the presence of sodium ethoxide afforded ethyl 3-acetyl-6-hydroxy-4-methyl-2(1H) pyridone-5-carboxylate derivatives (IVa,b,d). On the other hand, reaction of Ib,c,d with ethyl acetoacetate in tetrahydrofuran in the presence of sodium hydride did not give IV, but gave 3-acetyl-1-alkyl-5-(N-alkylcarbamoyl)-6-hydroxy4-methyl-2(1H) pyridone (VIb,c,d). Mechanisms for the formation of compounds IV and VI are discussed.     

Supermesityl-stabilisierte Iminoborane

Supermesityl stabilized Iminoboranes Amino-iminoboranes R′(SiMe₃)N–B≡N–R: IIc (R′ = CHMe₂), IId (R′= CMe₃) and IIe (R′ = SiMe₃) carrying the supermesityl group (R) on the imino nitrogen atoms have been prepared from the corresponding fluorobis(amino)boranes Ic–e by HF-elimination using t-BuLi (IIc, d) or n-lithio-bis(trimethylsilyl)amid (IIe) . The Amino-iminoboranes are thermally stable at room temperature. Upon treatment of the fluorobis(amino)boranes Ia, Ib, Ie with t-BuLi, LiF and HN(SiMe₃)R′ are eliminated and the B-t-butyl substituted iminoborane III is formed. The compounds are characterized by elementar analyses and spectroscopic data (MS, IR, NMR). An X-ray diffraction study has been performed for II d .     

Radical ring-opening polymerization behavior of vinylcyclopropanes derived from dienes and chloroform

1,1-Dichloro-2-vinylcyclopropane ( Ia ), 1,1-dichloro-2-methyl-2-vinylcyclopropane ( Ib ), 1,1,2-trichloro-2-vinylcyclopropane ( Ic ) were prepared from the corresponding dienes and chloroform in the presence of a phase transfer catalyst (PTC), R₄N⁺Cl^?. Monomers Ia – Ic underwent a clean 1,5-type radical ring-opening process to afford the corresponding polymers in good yield. Further, the relative rate of polymerization and reaction of ( I ) with thiophenol were studied.     

Temperature effects on the aggregation of decylpyridinium chloride in aqueous solution

Surface tension and conductivity measurements were used to study micelle formation in an aqueous solution of decylpyridinium chloride at 20, 25, 30, 35, and 40°C. The critical micelle concentration (CMC) was minimum at about 30–35°C. After CMC₁, aggregation with CMC₂ and CMC₃ occurred as the concentration increased.     

Synthesis and properties of quaternary ammonium Gemini surfactants with hydroxyl groups

The article describes synthesis of four hydroxyethyl alkylene–double alkyl bromide through substitution of nucleophilic d iethanolamine, 1-bromododecane, and 1,4-dibromobutane. The structure of the new hydroxyl cationic surfactant (HDCS) was characterized by ¹H NMR and FTIR spectra. The aqueous solution of HDCS showed critical micelle concentration, i.e., 5.6 × 10^?2 mM, and could reduce oil/water interfacial tension to 3.28 × 10^?3 mN m^?1. The surface tension measurements provided a series of parameters, including critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), adsorption efficiency (pC₂₀), and effectiveness of surface tension reduction (Π_CMC). In addition, maximum surface excess concentration (Г_max) and minimum surface area/molecule (A_min) at the air/water interface were obtained by the Gibbs adsorption isotherm. The influence of inorganic salts (sodium chloride, calcium chloride) and organic salts (sodium benzoate) on the surface tension of HDCS in aqueous solution was investigated. For wettability alteration measurement, contact angle measurement as a quantitative method was utilized. Meanwhile, foam ability, foam stability, and emulsifying property of the synthesized surfactant were also examined at different concentration. HDCS also had excellent viscosity property.     

阴离子孪连表面活性剂的合成及其表/界面活性研究

合成了疏水链长度不同和连接基长度不同的7种系列阴离子孪连表面活性剂,研究了它们的表/界面活性。结果表明,它们有较低的表面张力和临界胶束浓度(CMC),有很好的表面活性。它们的CMC都在10-5~10-6mol/L之间,表面张力在26·5~34mN/m之间。它们有非常好的抗一价、二价盐的能力。除了C16-C2-C16在高于5%的NaCl溶液中会产生析出外,其余孪连表面活性剂都能耐盐20%以上。随着盐浓度的增加,孪连表面活性剂与烷烃间的界面张力逐渐降低,能达到10-3mN/m。与中原油田原油间的界面张力能降低到10-3~10-4mN/m,表明它们可应用于特高矿化度油藏提高采收率。