Hydroxylamines Synthesis Essay

On By In 1

General

The monomode microwave reactions were carried out in a CEM Discover Microwave. Multimode microwave reactions were done in a Kennmore Microwave Oven (Household) Output: 1100 Watts (Frequency: 2450 MHz). All Gas Chromatograph Mass Spectrometry (GC-MS) was performed using a Shimadzu GC-17A and GCMS-QP5050A Labsolutions system. All reagents were purchased from Aldrich Chemical Company and were used without further purification. Since two different methods are described in this article Method 1 will refer to synthesis carried out under monomode conditions, while, Method 2 will refer to synthesis under multimode conditions. Only the GCMS data is given, however unsubstituted cyclic imides data matched that reported earlier [15].

Phthalimide (1): Method 1. Phthalic anhydride (0.20 g, 1.35 mmol), NH2OH·HCl (0.09 g, 1.30 mmol), and DMAP (0.04 g, 0.33 mmol) were thoroughly mixed in a CEM vial with a stirrer. This was capped and heated in a CEM Discover microwave for 5 minutes at 150 oC. This was rapidly cooled to room temperature yielding a dark brown solid. The reaction mixture was dissolved in AcOEt (4 mL) and was washed with distilled water (2 x 2 mL). The organic layer was concentrated to obtain a white solid (0.14 g, 70%); MS m/z 147 (M+) 104, 76, 50.

Phthalimide (1): Method 2. Phthalic anhydride (1.0 g, 6.75 mmol), NH2OH·HCl (0.54 g, 7.7 mmol), and DMAP (0.08 g, 0.65 mmol) were mixed in an 8 mL Teflon capped vial. The mixture was allowed to heat for 4 minutes and 11 seconds at 30 percent power in the multimode microwave and then cooled to room temperature. The sample was dissolved in acetone and flash chromatographed using silica (~30 g) with pure acetone as the mobile phase to obtain a yellow solid. Yield: 0.96 g (97%); MS m/z 147 (M+) 104, 76, 50.

Succinimide (2): Method 1. Succinic anhydride (0.20 g, 2.00 mmol), NH2OH·HCl (0.14 g, 2.0 mmol), and DMAP (0.04 g, 0.33 mmol) were thoroughly mixed in a CEM vial with a stirrer. This was capped and heated in a CEM Discover microwave for 5 minutes at 150 °C. This was rapidly cooled to room temperature yielding a dark brown solid. The reaction mixture was dissolved in AcOEt (4 mL) and was washed with distilled water (2 x 2 mL). The organic layer was concentrated to obtain a white solid (0.14 g, 71%); MS m/z 99 (M+) 56.

Succinimide (2): Method 2. Succinic anhydride (1.0 g, 10 mmol), NH2OH·HCl (0.80 g, 11 mmol), and DMAP (0.12 g, 0.98 mmol) were mixed in an 8 mL Teflon capped vial. The mixture was allowed to heat for 1 minute 49 seconds at full power in the multimode microwave and then cooled to room temperature. The sample was dissolved in acetone and flash chromatographed using silica (~30 g) with pure acetone as the mobile phase to obtain a yellow solid (0.95 g, 96%); MS m/z 99 (M+) 56.

cis-1,2-Cyclobutanedicarboximide (3): Method 1. cis-1,2-Cyclobutanedicarboxylic acid anhydride (0.20 g, 1.59 mmol), NH2OH∙HCl) (0.11 g, 1.58 mmol), and DMAP (0.04 g, 0.33 mmol) were thoroughly mixed in a CEM vial with a stirrer. This was capped and heated in a CEM Discover microwave for 5 minutes at 150 °C. This was rapidly cooled to room temperature yielding a white solid. The reaction mixture was dissolved in AcOEt (4 mL) and was washed with distilled water (2 x 2 mL). The organic layer was concentrated to obtain a white solid (0.12 g, 61%); MS m/z 125 (M+) 82, 54.

cis-1,2-Cyclobutanedicarboximide (3): Method 2. cis-1,2-Cyclobutanedicarboxylic acid anhydride (1.0 g, 7.9 mmol), NH2OH∙HCl (0.63 g, 9.1 mmol), and DMAP (0.10 g, 0.82 mmol) were mixed in an 8 mL Teflon capped vial. The mixture was allowed to heat for 1 minute 12 seconds at full power in the multimode microwave and then cooled to room temperature. The sample was dissolved in acetone and flash chromatographed using silica (~30 g) with pure acetone as the mobile phase to obtain a light brown solid, (0.95 g, 96%); MS m/z 125 (M+) 82, 54.

3a,4,5,6,7,7a-Hexahydro-1H-isoindole-1,3(2H)-dione (4): Method 1. cis-1,2-Cyclohexanedicarbo-xylic acid anhydride (0.20 g, 1.30 mmol), NH2OH∙HCl (0.09 g, 1.29 mmol), and DMAP (0.04 g, 0.33 mmol) were thoroughly mixed in a CEM vial with a stirrer. This was capped and heated in a CEM Discover microwave for 5 minutes at 150 °C. This was rapidly cooled to room temperature yielding a white solid. The reaction mixture was dissolved in AcOEt (4 mL) and was washed with distilled water (2 x 2 mL). The organic layer was concentrated to obtain a white solid (0.12 g, 61%); MS m/z 153 (M+) 125, 99, 82, 67, 54, 41.

3a,4,5,6,7,7a-Hexahydro-1H-isoindole-1,3(2H)-dione (4): Method 2. cis-1,2-Cyclohexanedicarboxylic acid anhydride (1.0 g, 6.5 mmol), NH2OH∙HCl (0.51 g, 7.3 mmol), and DMAP (0.08 g, 0.65 mmol) were mixed in an 8 mL Teflon capped vial. The mixture was allowed to heat for 1 minute 49 seconds at full power in the multimode microwave and then cooled to room temperature. The sample was dissolved in acetone and flash chromatographed using silica (~30 g) with pure acetone as the mobile phase to obtain a white solid (0.83 g, 84%); MS m/z 153 (M+) 125, 99, 82, 67, 54, 41.

Glutarimide (5): Method 1. Glutaric anhydride (0.20 g, 1.75 mmol), NH2OH∙HCl (0.12 g, 1.73 mmol), and DMAP (0.04 g, 0.33 mmol) were thoroughly mixed in a CEM vial with a stirrer. This was capped and heated in a CEM Discover microwave for 5 minutes at 150 °C. This was rapidly cooled to room temperature yielding a dark brown solid. The reaction mixture was dissolved in AcOEt (4 mL) and was washed with distilled water (2 x 2 mL). The organic layer was concentrated to obtain a light brown solid (0.12 g, 61%); MS m/z 113 (M+) 70, 42.

3a,4,7,7a-Tetrahydro-4,7-ethano-1H-isoindole-1,3(2H)-dione (6): Method 1. cis-Bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic acid anhydride (0.10 g, 0.56 mmol), NH2

Organic Chemistry Portal

Reactions > Organic Synthesis Search

Categories: N-O Bond Formation >

Synthesis of hydroxylamines and related compounds

Related:


Recent Literature


A copper-catalyzed electrophilic amination of simple and functionalized aryl, heteroaryl-, benzyl, n-alkyl, sec-alkyl, and tert-alkyl diorganozinc nucleophiles with R2NOC(O)Ph and RHNOC(O)Ph reagents as electrophilic nitrogen sources provides tertiary and secondary amines, respectively, in generally good yields.
A. M. Berman, J. S. Johnson, J. Org. Chem., 2006, 71, 219-224.

"); } document.write (""); window.onresize = divsize; function divsize() { width=window.innerWidth-215; if (width > 1000){document.getElementById("jobs").style.visibility = "visible"; width = width - 185;} else {document.getElementById("jobs").style.visibility = "hidden";} size=width+"px"; if (width < 710) {size=window.innerWidth-25+"px";} document.getElementById("content").style.width = size; document.getElementById("banner").style.width = size; }

0 comments

Leave a Reply

Your email address will not be published. Required fields are marked *