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Methanol and Acetone Is in Organic Synthesis

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Methanol and Acetone Is in Organic Synthesis Honeywell Burdick & Jackson® Characterization and Evaluation of Technical Grade Solvents and Comparison to their Purified Counterparts S. Lorenz, M. Bosma, A. Kemperman, V. Mohan and J. Przybytek Abstract: Technical grade solvents and their purified counterparts are separately useful for many different applications. One important application for the common solvents acetonitrile, methanol and acetone is in organic synthesis. Another important application for acetonitrile and methanol is as a diluent or mobile phase in chemical analysis, ie: UV-VIS spectroscopy, HPLC and LC-MS. We have observed and identified a number of impurities in these solvents that may interfere with synthesis and/or accurate analytical testing. For instance, a common contaminant in acetonitrile is acrylonitrile. Trace aldehydes and ketones can be found in methanol. Diacetone alcohol is commonly found in acetone. We have characterized impurity levels in commonly used solvents and will show the variability present in technical grade and purified solvents, using GC, GC-MS and LC-MS. Results on the impurities and their probable effect on synthesis and analytical testing will be presented. METHANOL HPLC Comparison of Methanol Grades HPLC Trace using HPLC Trace using HPLC Method Technical Grade Methanol Purified Methanol 0.200 0.200 Time % % 0.190 0.190 0.180 0.180 (min) Water Methanol 0.170 0.170 0.160 0.160 0.150 0.150 0 95 5 0.140 AU) 0.140 AU) ( ( 0.130 0.130 e e 20 0 100 c 0.120 c 0.120 n 0.110 n 0.110 a a b 0.100 b 0.100 r r 25 0 100 o 0.090 o 0.090 s s 0.080 0.080 b b A 0.070 A 0.070 30 95 5 V 0.060 V 0.060 U 0.050 U 0.050 0.040 0.040 35 95 5 0.030 0.030 0.020 0.020 0.010 0.010 Method/Instrument parameters: 0.000 0.000 Column: B&J HLD Octyl OC5 (C8) 0.00 0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 Column (15 X 0.46cm, 5um #9511) Minutes Minutes Flow Rate: 1.5mL/min Water used: Honeywell B&J Brand Methanol has applications in purge and trap and headspace analysis of various samples, including in environmental Water, #365-4 and drug sample analyses. It is also important in HPLC and GC applications. UV absorbance at 220 nm Comparison of Methanol Grades by GC with Electron Capture Detector • The ECD detector is selective for electronegative compounds, such as halogens, organometallic compounds, nitriles and nitro compounds. • The contamination peaks in the technical grade methanol detected by ECD range from 0.1-54pg (based on heptachlor epoxide as the standard). While the contamination peaks in the purified methanol are less than 0.3pg (based on heptachlor epoxide as the standard). • Note the solvent front interference and many large contamination peaks in technical grade methanol are absent in the purified methanol. Technical Grade Purified 500 500 ) ) s s t t n n u 400 u 400 o o C C D D C 300 C 300 E E ( ( y y t i t i s s n 200 200 n e e t t n I n I 100 100 0 5 10 15 20 25 0 5 10 15 20 25 Time (min) Time (min) Method: 200mL of methanol was concentrated (400x) and exchanged into hexane. The data was obtained on an Agilent 6890N GC with an ECD detector and a Restek Rtx-5 30 meter column. Sample injection = 5 microliters. The initial oven temperature was held at 200°C for 15 minutes then increased by 10°C/min until 250°C, then held for 10 minutes. Common Impurities in Technical Grade Methanol Some impurities that are commonly present in technical grade methanol are: 2-butanone (MEK), 3-pentanone, N, N-dimethyl acetamide and 2,3-butanedione. These are detectable by GC-MS in the technical grade material, indicating that their concentration is at least 1ppm. However, these impurities are not detected by GC-MS in purified methanol. Page 1 of 3 ACETONITRILE Lot-to-Lot Variablility in Acetonitrile Grades The following graphs show the variability which is normally seen in different lots of technical grade acetonitrile as well as the decrease in variability of purified acetonitrile. Data from 31 consecutive lots of technical grade acetonitrile and 31 consecutive lots of purified acetonitrile were collected and graphed. Lot-to-Lot Variability in Water Concentration Lot-to-Lot Variability in UV Absorbance in Technical Grade and Purified Acetonitrile of Technical Grade and Purified Acetonitrile 70 0.09 Purified Acetonitrile Purified Acetonitrile ) 0.08 60 Technical Grade Acetonitrile m Technical Grade Acetonitrile n m 5 p 0.07 2 p ( 2 50 ) n t s 0.06 o a i t i t e a n r 40 c 0.05 t u n n . a e s c b 0.04 b r n 30 a o ( o s C 0.03 b r 20 e A t 0.02 a V W 10 U 0.01 0 0 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 Lot Lot Lot-to-Lot Variability in Water Concentration. The water concentration was Lot-to-Lot Variability in UV Absorbance at 225nm. UV Absorbance was measured by Karl-Fisher Titration. determined with a Varian Cary 400 Scan UV-Visible Spectrophotometer utilizing a path length of 1 cm. • Low water content is very important in applications such as automated DNA/RNA synthesis and organic synthesis since the water may compete with the reactants in the reaction pathway. • UV absorbance background is critical for HPLC acetonitrile for two reasons: First, most organic impurities contribute to UV absorption. Second, the most commonly used detection mode in HPLC instruments is the UV detector, which means the lower the UV absorbance of acetonitrile, the lower the chromatographic baseline background, and hence the higher the sensitivity and the lower the detection limit. Spectral Comparison of Acetonitrile Grades UV Comparison of Acetonitrile Grades HPLC Comparison of Acetonitrile HPLC Method 0.99 0.200 0.190 Time % % 0.180 Purified Acetonitrile Purified Acetonitrile (min) Water Acetonitrile 0.170 Technical Grade Acetonitrile 0.160 Technical Grade Acetonitrile 0.150 0 70 30 0.140 AU) ( AU) ( 0.130 e e 0.120 c 5 70 30 c n 0.110 n a a 0.100 0.49 b r b r 0.090 o 15 30 70 o s 0.080 s b b 0.070 A A 0.060 20 30 70 V V 0.050 U U 0.040 0.030 25 70 30 0.020 0.010 -0.01 0.000 30 70 30 190 240 290 340 -0.010 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 Method/Instrument parameters: Wavelength (nm) Minutes Column: B&J OD5 (C18) (#9575) (25 X 4.6cm, 5mm) This graph shows a comparison of the typical absorbance of HPLC Chromatograms at 200 nm for technical grade and Flow Rate: 1.0 mL/min a technical grade acetonitrile sample and that of its purified purified acetonitrile. Water used: Honeywell B&J Brand Water, #365-4 counterpart. This data was obtained with a Varian Cary 400 Scan UV-Visible Spectrophotometer utilizing a path length of 5 cm. The higher absorbance between 240 and 195 nm is indicative of contaminants in the technical grade acetonitrile. Common Impurities in Technical Grade Acetonitrile Impurities Detected by Approximate Concentration Approximate Concentration GCMS* in Technical Grade in Purified Grade O NH2 Acetamide 5-20ppm Not Detected 3-Methyl-1-Butene 2-10ppm Not Detected N N 4-Methyl-4H-1,2,4-Triazole 2-10ppm Not Detected N O N 5-Methyl-3-Propyl-Isoxazole Not detected-5ppm Not Detected Data was collected on a Shimadzu QP2010 GCMS using A Restek Rtx-1 105m X 0.32mm column. The temperature program started at 60°C and progressed to 260°C at 5°C/min. *Detection limit approximately 1ppm. Page 2 of 3 ACETONE Comparison of Diacetone Alcohol Levels in Acetone Grades Most chromatographers find ketones, such as acetone, stable and easy to use. However, lower detection limits have created conditions in which solvent degradation effects are important. Ketones degrade over time through an acid or base catalyzed condensation. For acetone, the ketone reacts with its enol tautomer, to produce diacetone alcohol. This can undergo further reaction such as dehydration to produce mesityl oxide. High levels of diacetone alcohol may indicate material which has undergone degradation and may interfere with GC-FID and other sensitive instrumentation techniques. Technical Grade Purified 2000 2 1.8 1.6 ) ) 1500 m m p p 1.4 p p ( ( n n 1.2 o o i i t t a a 1000 1 r r t t n n 0.8 e e c c n n o 0.6 o 500 C C 0.4 0.2 0 0 1 5 9 13 17 21 25 29 33 1 2 3 4 5 6 7 8 Lot Lot The first graph shows the large variability in the concentration of the impurity diacetone alcohol in technical grade acetone.
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