24265-37-0

Upstream product

• 77568-66-2 2,2,2-trifluoroethanol-d₁ 
• 159562-64-8 C₁₈H₁₄F₆NO₄^(1-) 
• 159562-66-0 C₁₈H₁₇F₃NO₄S^(1-) 
• 159562-65-9 C₁₇H₁₅F₃NO₄^(1-) 
• 75-89-8 2,2,2-trifluoroethanol 
• 87191-88-6 2-oxo-ethen-1-id-1-yl 

Downstream Products

• 75-89-8 2,2,2-trifluoroethanol 
• 41084-91-7 deprotonated ketene anion 
• 460-43-5 2,2,2-trifluoroethyl methyl ether 
• 159562-65-9 C₁₇H₁₅F₃NO₄^(1-) 
• 159562-64-8 C₁₈H₁₄F₆NO₄^(1-) 
• 1163712-01-3 C₇H₈P^(1-) 
• 14609-74-6 p-nitrophenolate 
• 406-95-1 2,2,2-trifluoroethyl acetate 
• 150723-10-7 1-Methoxy-4-[(2,2,2-trifluoro-ethoxy)-(2,2,2-trifluoro-ethylsulfanyl)-methyl]-benzene 
• 150723-09-4 1-[Bis-(2,2,2-trifluoro-ethoxy)-methyl]-4-methoxy-benzene 
• 108-89-4 picoline 
• 110-86-1 pyridine 
• 100-02-7 4-nitro-phenol 
• 141516-55-4 2,2,2-trifluoroethyl 4-nitrobenzenesulfonate 

Relevant academic research and scientific papers

Reactivity of the radical anion OCC-

The characteristic reactivity of the radical anion OCC- has been investigated in the gas phase at 298 K through determination of rate coefficients, products, and branching fractions for each of 29 ion-molecule reactions. A wide variety of reactions is observed including abstraction of H, H+, and H2+, nucleophilic displacement, charge transfer, and reactions involving electron detachment. Many of the reactions involve cleavage of the C--CO bond, consistent with the relatively small C--CO bond energy and the proposed1 electronic structure of the ground state anion in which both radical and charge are centered on the terminal carbon. Similarities are noted between the chemistry of OCC- and its neutral analogue OCC and between the chemistry of OCC- and the radical anions O- and o-C6H4-. Most reaction products observed are consistent with reaction mechanisms involving initial attack of the terminal carbon in OCC- on the neutral reaction partner. The gas-phase acidity of HCCO is bracketed between those of CH3NO2 and CH3CHO, yielding 1502 ± 8 > ΔGoacid(HCCO) ≥ 1463 ± 8 kJ mol-1 and 1531 ± 12 > ΔHoacid(HCCO) ≥ 1491 ± 12 kJ mol-1. Observation of H atom transfer from CH2Cl2 to OCC- indicates that ΔHof(OCC-) ≥ 148 ± 12 kJ mol-1 and gives a larger lower limit of ΔHoacid ≥ 1507 ± 15 kJ mol-1. These and related thermochemical values, including the hydrogen bond dissociation energy in HCCO, are compared with literature values.

Detection and kinetic characterization of SNV intermediates. Reactions of thiomethoxybenzylidene Meldrum's acid with thiolate ions, alkoxide ions, OH-, and water in aqueous DMSO

The reaction of thiomethoxybenzylidene Meldrum's acid (5-SMe) with thiolate and alkoxide ion nucleophiles is shown to proceed by the two-step addition-elimination SNV mechanism in which the tetrahedral intermediate accumulates to detectable levels. For the reactions with thiolate ions, rate constants for nucleophilic addition (k1RX), its reverse (k-1RX), and for conversion of the intermediate to products (k2RX) were determined. For the reactions with alkoxide ions, only k1RX and k-1RX could be obtained; the intermediate in these reactions did not yield the expected substitution products, and hence no k2RX values could be determined. The reaction with OH- and water are believed to follow the same mechanism, but the respective intermediates remain at steady-state levels, and only k1OH and k1H2O for nucleophilic attack on 5-SMe were measurable. New insights regarding structure-reactivity behavior in SNV reactions are gained from comparisons of rate and equilibrium constants in the reactions of 5-SMe with the corresponding parameters in the reactions of methoxybenzylidene Meldrum's acid (5-OMe) and benzylidene Meldrum's acid (5-H). In particular, the relative importance of steric and π-donor effects of the MeS vs. MeO group in 5-SMe and 5-OMe, respectively, and their role in affecting the intrinsic rate constants for nucleophilic addition, has been clarified by these comparisons. Our results also add support to a previous suggestion that soft-soft type interactions tend to increase intrinsic rate constants for thiolate ion addition to vinylic substrates, especially 5-SMe with the soft MeS group.

Kinetic analysis of elementary steps in nucleophilic vinylic substitution reactions of α-nitro-β-X-stilbenes (X = OCH2CF3, OCH3, NO2) with various nucleophiles.

Rate constants of elementary steps in the addition-elimination mechanism of nucleophilic vinylic substitutions (SNV) were determined by studying the following reactions in 50% Me2SO-50% water at 20 °C: (1) α-nitro-β-(2,2,2-trifluoroethoxy)stilb

GAS PHASE SULFUR ANIONS: SYNTHESIS AND REACTIONS OF H2NS(1-) AND RELATED IONS

Many gas-phase anions react with carbonyl sulfide by sulfur atom transfer to form RS(1-) ions.The properties of H2NS(1-), formed in this way from H2N(1-) and OCS, are described.