Synthesis of tetrakis (pyrrolidino) phosphonium tetrafluoroborate (Py4P1+BF4-), tetrakis (piperidino) phosphonium tetrafluoroborate (Pi4P1+BF4-), and tetrakis (morpholino) phosphonium tetrafluoroborate (Mo4P1+BF4-).
Stoichiometric pyrrolidino, piperidino, and morpholino were reacted with PCl5 in absolute CH2Cl2 or chlorobenzene at various temperatures. After the completion of the reactions, NH4BF4/H2O was added at room temperature. The resulting products were washed with solvents, and the white solids thus obtained were isolated by filtration and dried in vacuum. The reactions with three phosphonium salts are shown by Equations (2), (3), and (4). 1H-NMR (Py4P1+BF4-, 400MHz, CDCl3, 30 °C, TMS): δ = 1.94 ppm (m. 16H. NCH2CH2), 3.21 ppm (m,
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1H-NMR (P5+BF4-, 400MHz, CDCl3, 30 °C, TMS): δ = 2.60 ppm (m, 72H, CH3). (Figure S6); IR (KBr): 2934 (s), 2819 (s), 1472 (m), 1397 (w), 1301 (w), 1219 (m), 1103 (vs), 1058 (vs), 978 (vs), 745 cm-1 (w) (Figure S1); MS (ESI) m/z: calcd for C24H72N16P5Cl, 774.4497; found, 774.3795.
2.2.4 Synthesis of phosphonium methanol (P+CH3O-)
Phosphonium tetrafluoroboron salts were dissolved in anhydrous methanol and stirred at room temperature. Stoichiometric potassium methoxide was added to the flask, and the precipitated KBF4 was filtered off after reaction for 2 h, and the methanolic solution was reserved.
2.3 Ring-opening polymerization of PO
Glycerol was partially deprotonated with the P+CH3O- by distilling off methanol under vacuum at 70 °C for 1 h in a sealed glass vessel (50 mL), and dried overnight at 110 °C). Stoichiometric PO was pushed into a vessel set in a pre-heated oil-bath for polymerization, cooled to room temperature, and the residual monomer was removed by evaporation when the polymerizations were finished. Excess methanol and cation exchange resin (Amberlite IR-120) were added to the crude products and stirred at 25 °C for 1 h. Purified PPOs were obtained after filtration and removal of methanol, and characterized by NMR (1H and 13C) spectroscopy and gel permeation chromatography
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The catalysts were mixed with a KBr salt pellet. FTIR spectra were generated from 32 scans in the wavenumber range 4000–400 cm-1 at a resolution of 4 cm-1.
2.4.2 NMR
1H NMR and 13C NMR spectra were recorded using a Bruker Biospin AG, Magnet System 400 MHz/54 mm spectrometers at 25 °C, using chloroform-d (CDCl3) as the solvent and trimethylsilane as the internal standard.
2.4.3 Gel Permeation Chromatography (GPC)
GPC Measurements were performed using a Waters 1515 Isocratic HPLC using tetrahydrofuran (THF) as an eluent at 35 °C, at a flow rate of 1.0 mL/min. The polymers were dissolved in THF at a concentration of 6 mg/mL. The system was calibrated using a series of monodisperse linear PPO standards with molecular weights in the range 200–12000 g/mol.
2.4.4 Electrospray ionization mass spectrometry (ESI-MS)
ESI-MS Measurements were performed using a Micromass LCTTM Liquid Chromatography/Time-of-Flight Mass Spectrometer equipped with a Waters 600 Liquid Chromatography System.
2.4.5 The degree of unsaturation (C=C)
The degree of unsaturation was calculated by 1H-NMR. 1H-NMR (PPO, 400 MHz, CDCl3, TMS): δ = 1.12 ppm (m. CH3), 3.20–3.80 ppm (CH2, CH), 3.13 ppm (CH2CHOH), 3.90 ppm (CH2CHOH), 5.14 ppm (CH2=CH-CH2), 5.27 ppm (CH2=CH-CH2), 5.87 ppm (CH2=CH-CH2) (Figure
After 10 minutes the reaction liquid was separated from the solid using a vacuum filtration system and toluene. The product was stored and dried until week 2 of the experiment. The product was weighed to be 0.31 g. Percent yield was calculated to be 38.75%. IR spectra data was conducted for the two starting materials and of the product. Melting point determination was performed on the product and proton NMR spectrum was given. The IR spectrum revealed peaks at 1720 cm-1, which indicated the presence of a lactone group, and 1730 cm-1, representing a functional group of a carboxylic acid (C=O), and 3300cm-1, indicating the presence of an alcohol group (O-H). All three peaks correspond with the desired product. A second TLC using the same mobile and stationary phase as the first was performed and revealed Rf Values of 0.17 and 0.43for the product. The first value was unique to the product indicating that the Diels-Alder reaction was successful. The other Rf value of 0.43 matched that of maleic anhydride indicating some
Using SN1 reaction mechanism with hydrochloric acid, t-Pentyl alcohol was converted to t-Pentyl chloride in an acid catalyzed reaction. The reaction took place in a separatory funnel designed to separate immiscible liquids. The crude product was extracted by transferring a solute from one solvent to another. The process of washing the solutions by phase transfer was used in order to remove impurities from the main solvent layer. Finally, the crude product was dried with anhydrous Calcium chloride and purified once more by simple distillation technique.
The purpose of this lab was to carry out a dehydration reaction of 2-methylcyclohexanol by heating it in the presence of phosphoric acid and determining which alkene product would be the major product. Methylcyclohexanols were dehydrated in an 85% phosphoric acid mixture to yield the minor and major alkene product by elimination reaction, specifically E1. The alkenes were distilled to separate the major and minor products and gas chromatography was used to analyze the results and accuracy of the experiment. The hypothesis was the major product of the reaction would be the most substituted product. This conclusion was made because of
Objective: The objective of this experiment is to use acid-base extraction techniques to separate a mixture of organic compounds based on acidity and/or basicity. After the three compounds are separated we will recover them into their salt forms and then purify them by recrystallization and identify them by their melting points.
There are four main regions of IR absorptions: region 4000 – 3000 cm-1 corresponds to N-H, C-H and O-H stretching, region 2250- 2100 cm-1 is triple-bond stretching , region 2000- 1500 cm-1 is double bonds and the region below 1500 cm-1 is the fingerprint region where a variety of single bonds are absorbed.3 The chromic acid test is a test for oxidizability and gives a positive result for primary and secondary alcohols as well as aldehydes2. A positive result in the chromic acid test is indicated by a color change and the formation of a precipitate. Tertiary alcohols give negative results for the chromic acid test since there must be a hydrogen present on the alcoholic carbon for oxidation to occur. The 2,4 DNP test, tests for a carbonyl and is therefore a dependable test for aldehydes and ketones. Finally, 13C NMR spectroscopy is a test to determine the structure of a compound. 13C NMR detects the 13C isotope of carbon. Each carbon has a different chemical shift. A carbon’s chemical shift is affected by the electronegativity of nearby atoms. Carbons that are bonded to highly electronegative atoms resonant downfield because the electronegative atom pulls electrons away from the nearby carbons and cause those carbons to resonant downfield1 (John McMurry, 2008). A general trend is that sp3-hybridized carbons absorb from 0 to 90 ppm, sp2-hybridized carbons resonant between 110
Chemistry Central Journal 7.1 (2013): 1-11. Academic Search Complete. Web. 12 Feb. 2015. Osser, Edek. "
Through the use of the Grignard reaction, a carbon-carbon bond was formed, thereby resulting in the formation of triphenylmethanol from phenyl magnesium bromide and benzophenone. A recrystallization was performed to purify the Grignard product by dissolving the product in methanol. From here, a melting point range of 147.0 °C to 150.8 °C was obtained. The purified product yielded an IR spectrum with major peaks of 3471.82 cm-1, 3060.90 cm-1, 1597.38 cm-1, and 1489.64 cm-1, which helped to testify whether the identity of the product matched the expected triphenylmethanol. The identity of the product being correct was further confirmed by way of both proton and carbon-13 NMR spectra. This is due to the fact
The result from the IR spectra for Trans-[Bis(inosinato)palladium(II)], and inosine are summarized in Table 2 and 3. It is important to note that Trans-[Bis(inosinato)palladium(II)] compound had an extra carbonyl peak at 1712.21 cm-1 which is from inosine impurity.
One milliliter of 6.00-M phosphoric acid was placed into a 125-mL Erlenmeyer flask using a volumetric pipette. Using a slightly larger pipette, six milliliters of 3.00-M sodium hydroxide was transferred into a 50-mL beaker. Then a disposable pipette was used to slowly mix the sodium hydroxide into the phosphoric acid while the solution was swirled around. Then both the beaker and flask were rinsed with 2-mL of deionized water and set aside. A clean and dry evaporating dish was weighed with watch glass on a scale. Then the solution was poured into the dish and the watch glass was placed on top. The solution was then heated with a Bunsen burner to allow for the water to boil off to reveal a dry white solid. After the dish cooled to room temperature it was once again weighed and the new mass was recorded.
For this experiment, unknown sample 10 was given with the empirical formula of C4H10O. Several scans were conducted in order to discover the unknown alcohol sample. After obtaining the 1H NMR spectra of sample 10, 1H NMR signals and 13C NMR were used to determine the structure of the alcohol. The results of the 1H NMR displayed the total signals, chemical shift, multiplicity and the integration of sample 10. The chemical shift tells the electron environment near the 1H nucleus*. When near a electron withdrawing group 1H nucleus is deshielded and is shifted downfield towards a higher ppm which gives evidence to atom "A" being near an electronegative atom with an peak observed of 5.00. In addition, according to the 1H NMR chemical shift table a ppm of 2-5 represents a R-OH which coin side with atom "A" near an oxygen. Furthermore, Signal splitting otherwise known as multiplicity tells us the number of nuclei or hydrogen neighbors are on a particular molecule. Signals "B" the spectra illustrated
Olmsted, John III; Williams, Greg; Burk, Robert C. Chemistry, 1st Canadian ed.; John Wiley and Sons Ltd: Mississauga, Canada, 2010, pp 399 - 406
Perfluorocarbons (PFCs) are lab made chemical compounds that are linear and cyclic hydrocarbons who have a low molecular weight. Liquid Perfluorocarbons are formed when hydrogen ions in hydrocarbons have been replaced with fluorine atoms since they are neutral chemical compounds (Veni et al. 39). Perfluorocarbons are also chemically inert—not chemically reactive—due to the strength of the carbon-fluorine bonds (Anilkumar et al. 478). Perfluorocarbons are made into Perfluorocarbon artificial blood by adding water, salt and phospholipid surfactants to it, then the solution is then emulsified through high pressure homogenization—when two non-soluble liquids are turned into an emulsion—the solutions is then purified through a high temperature
The retained solution from the NaHCO3 extraction was used to precipitate the P-toulic acid. Drop wise 3M HCl was added to the extracted solution carefully until no more precipitate was formed and the solution tested acidic, with a pH reading less than 3 as indicated by pH paper testing. A piece of clean filter paper was then weighed and the mass recorded in a lab notebook. A vacuum filtration system was constructed with a Buchner funnel
-The deuterated methanol is represented as MeOH-d4 and in some places it was presented as CD3OD, restricting to any one of the form is most appropriate. Similarly, the NMR solvent DMSO should be represented as DMSO-d6 instead of DMSO.
The results from the NMR of 1-propanol showed 3 different prominent peaks with the peak at 2.2 cm-1 being the acetone. Because 1-bromopropane has three non-equivalent hydrogens it was found to represent this set of NMR data. The other product, 2-bromopropane only had 2 different types of hydrogens and would have only had 2 peaks. Further analysis of the structure of 1-bromopropane showed that the hydrogens closest the bromine group were an indication of peak A in the graph. Because of the electronegativity of the bromine, this peak was located further downfield. There were 2 neighboring hydrogens so using the n+1 rule gave the 3 peaks. Going down peak B showed the next carbon which had 5 neighboring hydrogens thus giving 6 peaks. Finally, the carbon furthest away from the bromine was found at peak C. It had 2 neighboring hydrogens and provided 3 peaks.