N‐Boc‐3‐pyrroline Boc‐diallyamine 1H‐Pyrrole‐1‐carboxylic acid, 2,5‐dihydro‐, 1,1‐dimethylethyl ester Triethylamine Ruthenium chloride Tris(hydroxymethyl)phosphine

Allylic phosphonium ylides are readily generated by the combination of an allylic alcohol, a carbene, and a chlorophosphite. Here we demonstrate that these intermediates undergo a thermal [3,3]-rearrangement to provide single isomers of homoallylic phosphonates in good to excellent yields. This new reaction manifold for phosphorus ylides is tolerant of a range of substitution patterns on the reactants and provides access to structurally complex intermediates for the synthesis of enzyme inhibitors, aminophosphonic acids, and natural products.

Currently, inverse emulsion (water-in-oil) polymers are the most widely applied friction reducers for hydraulic fracturing. While oil-external friction reducers are the industry standard, they are limited by their tolerance to water containing high Total Dissolved Solids (TDS), requiring low TDS in blended waters to achieve adequate friction reduction without the addition of an external surfactant to aid in hydration. To increase operational efficiency and reduce impact on local infrastructure, operators desire to recycle the maximum amount of produced water. To meet this goal, a friction reducer that functions unassisted in high TDS water is needed. This paper describes the use of a Dispersion Polymer Friction Reducer (DPFR) in the Marcellus Shale that addresses this need. A salt-tolerant, water-based friction reducer was developed to allow well operators to reuse high TDS produced waters encountered in the Marcellus Shale. Both lab and field experiments were carried out to assess the effectiveness of the new friction reducer. The data presented in this paper show several advantages of the DPFR: (1) conservation of fresh water sources, (2) greater flexibility in water source options, (3) reduced analytical testing for produced water management, and (4) rapid onset of friction reduction without need for external surfactants. The DPFR provided efficiency improvements to the service company through fewer chemicals required to achieve high pumping rates. The operator benefitted from having greater flexibility in use of produced, recovered and recycled waters. Laboratory flow loop tests indicated that the DPFR would be an effective friction reducer for a wide variety of water types, and this was confirmed by field testing as shown in the treatment plots included in this paper. Minor modifications in material handling procedures were required in the application of the DPFR. This paper details the collaboration between a chemical manufacturer, a service company and an operator which resulted in the successful development, testing and deployment of an innovative technology in the Marcellus Shale. The DPFR technology offers environmental, economic, and operational advantages over the previous inverse-emulsion polymer technology.

Natural gas plays a key role in meeting the energy demands of the United States, and the production of natural gas from tight shale formations is expanding rapidly as the demand for clean and efficient energy rises. Slickwater fracturing, a hydraulic fracturing technique whereby a water-based fluid is injected into a well at intense pressurescausing the formation rock to crack, or fracture-is the most commonly used stimulation technique in tight gas reservoirs. Slickwater fracturing treatments involve combining a base fluid with a friction reducer, a polymer that enables faster pumping of the fluid into the formation, and a propping agent, or proppant-a granular substance, such as sand, that is carried into the formation by the fluid and holds the fractures open once the treatment is complete.Each stage of a slickwater-fracturing treatment requires tens of thousands of barrels of fracturing fluid. Furthermore, each slickwater treatment generates a great deal of wastewater, as most of the fracturing fluid will flow back out of the well, and production brines, or produced water, will flow back over the long term. Programs for managing produced water are on the rise, as technology for convenient and economical treatment of wastewater improves. However, often the most cost-effective and convenient use of produced water is to reuse it in subsequent fracturing treatments.Evaluation of friction-reducer performance in the reused water is crucial because produced water from most of the US tight shale formations contains elevated levels of dissolved solids, compared with fresh or tap water. Reusing waters with high levels of total dissolved solids (TDS) can lead to adverse interactions between the friction reducer and the base fluid. The adverse interactions result in elevated treating pressures, and this is often overcome by introducing more of the friction reducer into the mixture, which leads to higher chemical costs for the treatment.An alternative to adding more friction reducer is to switch to one that is more compatible. Polymer technology Fig. 1-Friction-reducer performance in produced water from the Woodford shale (9.9% NaCl, 1.8% CaCl 2 , 0.4% MgCl 2 , 0.1% KCl, 0.08% SrCl 2 ); friction-reducer concentration=0.033%. 90 80 90 FR A 60 70 ction FR-A

Organo-phosphorus compounds S 0080 [3,3]-Rearrangements of Phosphonium Ylides. -The reaction of an allylic alcohol, a chlorophosphite like compound (I), and a carbene derived from a diazo compound affords allylic phosphonium ylides. These intermediates undergo a thermal [3,3] rearrangement to give single isomers of homoallylic phosphonates in good to excellent yields. -(FERGUSON, M. L.; SENECAL, T. D.; GROENDYKE, T. M.; MAPP*, A. K.; J.