Unsymmetrical diaryl sulfones through palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides

[reaction: see text] A simple and efficient method for the synthesis of unsymmetrical diaryl sulfones using the palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides has been developed. High product yields, a short reaction time, and mild reaction conditions are important features of this method.     

N2 Laser Excited Fluorescence of Oxalyl Chloride at 77°K

The N₂ laser excited fluorescence spectrum and the intensity of fluorescence of oxalyl chloride C₂O₂Cl₂) condensed at 77°K either alone, or, diluted with a non-hydrocarbon or a hydrocarbon with dilution ratios ranging from 10 to 100 were studied. A slow condensation of the hydrocarbon matrix diluted sample showed a considerable reduction in the fluorescence intensity as compared to a fast condensation of the same sample.     

Palladium catalyzed ligand-free Suzuki cross-coupling reactions of benzylic halides with aryl boronic acids under mild conditions

A highly efficient Suzuki cross-coupling reaction between benzylic halides and aryl boronic acids using palladium chloride as catalyst in acetone:water (3:1) as the solvent system has been developed. High yields of products, mild reaction conditions and short reaction times in the absence of ligand are important features of this method.     

A rotationally-resolved Rydberg transition of I2

Rotationally-resolved bands leading to a Rydberg state R 0 _u ⁺ of molecular I₂ are observed in a two-stage, three-photon transition from the ground state. The R 0 _u ⁺ state interacts homogeneously with high vibrational levels, ν_F ≈ 200–250, of an ionic state F 0 _u ⁺, the perturbation being directed by the vibrational overlap integrals towards even-numbered vibrational levels of R. Spectral constants of R 0 _u ⁺ are (in cm^-1): T _e = 61665·15, ω_e = 209.29, ω_e x _e = 0·859, B _e = 0·03842 and α_e = 1·6 × 10^-4. The electronic matrix element for the R, F interaction (excluding one deviant result) is |W _e| = 107 ± 1 cm^-1; thus W _e/ω_e ≈ 0·5, corresponding to ‘intermediate’ coupling. Energy considerations indicate that R should be assigned to the 0 _u ⁺ state of either the configuration (2430 Π_1/2g )6pσ _u , or of (2421 ⁴Σ _u ^-)6sσ _g . This state is the first extra-valence state of I₂ to be rotationally analysed.     

Polarization spectroscopy of ion-pair states of ICl

Molecular constants for the E0⁺(³P₂) and 1(³P₂) ion-pair states of ICl vapor have been determined using sequential two-photon polarization-labeling spectroscopy. The two states are coupled by a heterogeneous perturbation which is analyzed in some detail for low-lying vibrational levels of 1(³P₂). The I³⁵Cl potential constants for the 1(³P₂) state and the rotation-vibration constants for the set of f sublevels—i.e., the constants unaffected by coupling with the E state—are (in cm⁻¹) 1(³P₂): Y_0,0= 39103.814(32), Y_1,0= 170.213(15), Y_2,0= −0.4528(22), Y_3,0= −7.0(12) × 10⁻⁴, Y_4,0= −1.48(24) × 10⁻⁵ and Y_5,0= −6.6(19) × 10⁻⁸, Y^(f)_0,1= 5.6878(17) × 10⁻² Y^(f)_1,1= −2.110(24) × 10⁻⁴, Y^(f)_2,1= −1.23(62) × 10⁻⁷, and Y^(f)_0,1= −3.08(22) × 10⁻⁸Likewise, the I³⁵Cl constants determined for the E 0⁺(³P₂) state are E 0⁺(³P₂: Y_0,0= 39054.38(61), Y_1,0= 166.96(10), Y_2,0 = −0.3995(42), Y_0,1= 5.738(31) × 10⁻², and Y_1,1= −1.67(26) × 10⁻⁴Practical constraints in pumping the sequence E 0⁺ ← B 0⁺ ← × 0⁺ restrict the analysis of the E state to levels v = 9–15. Given the long extrapolation to the equilibrium state the 3σ statistical uncertainties quoted for these constants should be treated with caution.     

Polarization spectroscopy of ICl: The D′, a and a′ states

Three previously-unanalyzed states of ICl are reported, an ion-pair state D′(Ω =2) which converges to the limit I⁺(P₂+ Cl^-(S_o), and two shallow states a(Ω = 1) and a′(Ω = 0⁺) both of which converge to the ground states of separated atoms I(P_{$\text{3}\text{2}$}) + Cl(P_{$\text{3}\text{2}$}). The a(0⁺) state is responsible for the well-known interruption of the B(0⁺) state above υ_B = 3. Spectroscopic constants are given for the D′ and a′ states.     

Sequential two-photon spectroscopy of some ion-pair states of IBr

Molecular constants of the first E 0⁺ ion-pair state of IBr vapor have been determined using polarization-labeling spectroscopy applied to the sequential transitions E 0⁺ ← B′ 0⁺ ← X 0⁺, while the second f 0⁺ ion-pair state is reported and characterized for the first time. A least-squares, simultaneous analysis of data for the I⁷⁹Br and I⁸¹Br isotopes gives the following constants (in cm^?1) for I⁷⁹Br:

$\text{E}\text{state}\text{: T}{}_{\mathrm{<mtext>e</mtext>}}\text{= 39487.32(12), ω}{}_{\mathrm{<mtext>e</mtext>}}\text{= 119.518(21), ω}{}_{\mathrm{<mtext>e</mtext>}}\text{ξ}{}_{\mathrm{<mtext>e</mtext>}}\text{= 0.2109(12)}$

,

$\text{ω}{}_{\mathrm{<mtext>e</mtext>}}\text{y}{}_{\mathrm{<mtext>e</mtext>}}\text{= ? 2.34(22) × 10}{}^{\mathrm{?4}}\text{, B}{}_{\mathrm{<mtext>e</mtext>}}\text{= 2.9701(14) × 10}{}^{\mathrm{?2}}$

,

$\text{α}{}_{\mathrm{<mtext>e</mtext>}}\text{= 5.43(59) × 10}{}^{\mathrm{?5}}\text{,}\text{and}\text{γ}{}_{\mathrm{<mtext>e</mtext>}}\text{= ? 6.8(16) × 10}{}^{\mathrm{?7}}$

.

$\text{F}\text{state}\text{: T}{}_{\mathrm{<mtext>e</mtext>}}\text{= 45382.58(17), ω}{}_{\mathrm{<mtext>e</mtext>}}\text{= 128.805(66), ω}{}_{\mathrm{<mtext>e</mtext>}}\text{ξ}{}_{\mathrm{<mtext>e</mtext>}}\text{= 0.3630(69)}$

,

$\text{ω}{}_{\mathrm{<mtext>e</mtext>}}\text{y}{}_{\mathrm{<mtext>e</mtext>}}\text{= ? 9.7(22) × 10}{}^{\mathrm{?4}}\text{, B}{}_{\mathrm{<mtext>e</mtext>}}\text{= 3.0073(30) × 10}{}^{\mathrm{?2}}\text{,}\text{and}\text{α}{}_{\mathrm{<mtext>e</mtext>}}\text{= 8.52(48) × 10}{}^{\mathrm{?5}}$

. Preliminary data for the first $\text{Ω}\text{= 1}$ ion-pair state, accessed in the sequence $\text{1(}{}^3\text{P}{}_2\text{) ← A(}\text{Ω}\text{= 1) ← X 0}{}^{\mathrm{+}}$, indicate that T_e is ?30 cm^?1 higher in energy than that of the E state.     

Removal of unwanted fluid

This work is concerned with the removal of unwanted fluid through the source–sink pair. The source consists of fluid issuing out of a nozzle in the form of a jet and the sink is a pipe that is kept some distance from the source pipe. Of concern is the percentage of source fluid sucked through the sink. The experiments have been carried in a large glass water tank. The source nozzle diameter is 6 mm and the sink pipe diameter is either 10 or 20 mm. The horizontal and vertical separations and angles between these source and sink pipes are adjustable. The flow was visualized using KMnO₄ dye, planer laser induced fluorescence and particle streak photographs. To obtain the effectiveness (that is percentage of source fluid entering the sink pipe), titration method is used. The velocity profiles with and without the sink were obtained using particle image velocimetry. The sink flow rate to obtain a certain effectiveness increase dramatically with lateral separation. The sink diameter and the angle between source and the sink axes don’t influence effectiveness as much as the lateral separation.     

Evaporation From Confined Porous Media Due to Controlled IR Heating From Above

We report an experimental study of evaporation due to controlled infrared (IR) heating from above from an initially saturated confined porous medium consisting of nearly ‘mono-disperse’ particles which has been rarely used earlier. We have used three diagnostic tools simultaneously, evaporation rate measurements using a precision weighing balance, surface temperature measurements using IR imaging, and fluorescein dye mixed with water to visualize the drying front and the evaporation sites. IR images show that the first stage, so-called constant rate period (CRP), was maintained due to films of water reaching the top surface from the saturated region below. Gradually reducing evaporation rate in stage 1 is shown to be related to ‘shrinking evaporating patches’ on the top surface, clearly revealed as lower-temperature regions in the IR images. End of CRP coincides with disappearance of the low-temperature patches. We give end of CRP in terms of the average depth (L_cap) of the liquid level from the top surface at that time. L_cap and duration of CRP are strong functions of the porous medium bead size, transition to stage 2 happening earlier for coarser spheres. The obtained L_cap values deviated from the predictions of Lehmann et al. (Phys Rev E 77(5):056309, 2008) which we show is due to a small range of pore sizes in the current experiments. For both water and highly volatile n-pentane, we show that L_cap normalized by a length scale derived from gravity-surface tension force balance goes like Bo^0.20, for Bo varying from 2.0E ? 04 to 1.0E ? 01; Bo is the Bond number. Fluorescein dye imaging shows a different view of the evaporation stages. During CRP, highly concentrated deposits of the fluorescein dye particles, orange in colour, are seen in the top few bead layers. These orange deposits represent the sites on the beads surfaces where the evaporation has taken place. Even with external heating, evaporation from such a porous medium is limited to a finite depth from the evaporating end, similar to the observation by Lehmann et al. (2008) for isothermal evaporation in Hele-Shaw cell.