| 92% |
With [PdCl2{κ2-(P,N)-2-Ph2PC6H4CH=NOH}] In acetonitrile at 100℃; for 24h; Inert atmosphere; Sealed tube; |
|
| 91% |
With per-rhenic acid In water; toluene for 1h; Heating; |
|
| 91% |
With per-rhenic acid In water; toluene for 1h; Heating; |
|
| 89% |
With 1,1'-Thiocarbonyldi-2(1H)-pyridone In toluene for 0.5h; Heating; |
|
| 89% |
With oxalyl dichloride; dimethyl sulfoxide In acetonitrile at 20℃; for 2.5h; Inert atmosphere; |
3 3)Preparation of cyclohexanecarbonitrile
Nitrogen protection, in a 100 mL three-necked flask equipped with a thermometer,Anhydrous acetonitrile (10 mL), dimethyl sulfoxide (0.03 mmol,2.5 mg, 0.01 equiv) and oxalyl chloride (0.31 mL, 3.6 mmol,1.2equiv),Slowly add cyclohexylformaldehyde oxime (3 mmol, using a constant pressure dropping funnel at room temperature).A solution of 381 mg, 1.0 equiv) in dry acetonitrile (5 mL).After the dropwise addition for 30 minutes, stirring was continued for 2 hours, and the solvent was evaporated to obtain a crude product.Purified by column chromatography (petroleum ether / ethyl acetate = 9:1).291 mg of cyclohexonitrile was obtained in a yield of 89%. |
| 89% |
With oxalyl dichloride; triethylamine In dimethyl sulfoxide; acetonitrile at 20℃; for 1h; |
|
| 88% |
With oxalyl dichloride; Triphenylphosphine oxide In chloroform-d1 at 20℃; for 1h; |
4.3.1. Method a
General procedure: To a solution of triphenylphosphine oxide (14 mg, 0.050 mmol) in either CHCl3, CDCl3 or EtOAc (2.0 mL) was added oxalyl chloride (102 μL, 1.21 mmol) and the reaction mixture was stirred for 5 min. The appropriate oxime (1.00 equiv) as solution in either CHCl3, CDCl3 or EtOAc (1.0 mL) was then added over 0.5 h via syringe pump at room temperature and the reaction mixture was stirred for a further 0.5 h at room temperature after which the solvent was removed in vacuo. Purification by flash chromatography (silica, 10-100% Et2O/pet. ether) gave the pure nitriles. |
| 88% |
With bromethyl methyl ether; triethylamine In tetrahydrofuran for 0.666667h; Reflux; |
General procedure for the preparation of Nitriles (Entry 1-13)
General procedure: For the preparation of nitrile from aldoxime using amethoxymethyl bromide as the dehydration agent, Et3N(1.5 mmol) was added to a stirred mixture of aldoxime(1.0 mmol) and 10 mL of THF, followed by methoxymethylbromide (1.5 mmol). The resulting mixture was refluxed for aspecified period (Table 1). The reaction was monitored byTLC (ethyl acetate: petroleum ether, 1:1). After completion ofreaction, the contents were poured into water and neutralizedwith NaHCO3 solution (20 mL, 10%), and then extractedwith ethylacetate (10 mL x 3). The combined organic mixturewas dried over anhydrous Na2SO4, concentrated and theresidue was purified by column chromatography on silica gel(60-120 mesh) using ethyl acetate, and then the solvent wasremoved at reduced pressure to give products in 79%-96%yields (Entry 1-13). The nitriles characterized by LC-MS, 1HNMR and 13C NMR analysis. |
| 88% |
With bromethyl methyl ether; triethylamine In tetrahydrofuran for 0.666667h; Reflux; |
General procedure for the preparation of Nitriles (Entry 1-13)
General procedure: For the preparation of nitrile from aldoxime using a methoxymethyl bromide as the dehydration agent, Et3N (1.5 mmol) was added to a stirred mixture of aldoxime(1.0 mmol) and 10 mL of THF, followed by methoxymethyl bromide (1.5 mmol). The resulting mixture was refluxed for aspecified period (Table 1). The reaction was monitored byTLC (ethyl acetate: petroleum ether, 1:1). After completion ofreaction, the contents were poured into water and neutralized with NaHCO3 solution (20 mL, 10%), and then extracted with ethyl acetate (10 mL x 3). The combined organic mixture was dried over anhydrous Na2SO4, concentrated and theresidue was purified by column chromatography on silica gel(60-120 mesh) using ethyl acetate, and then the solvent was removed at reduced pressure to give products in 79%-96%yields (Entry 1-13). The nitriles characterized by LC-MS, 1H NMR and 13C NMR analysis. |
| 87% |
With trichloromethyl chloroformate In acetonitrile for 0.0833333h; |
|
| 85% |
With 4 A molecular sieve In acetonitrile at 80℃; for 0.25h; |
|
| 85% |
With gallium(III) trichloride In acetonitrile at 80℃; for 6h; Inert atmosphere; |
Synthesis of Nitriles from Oximes (Method 1A and 1B)A
General procedure: A solution of oxime (0.5 mmol) and SnCl2.2H2O (Method 1A, under open air) or GaCl3 (Method 1B, under argon) (0.05 mmol) in dry MeCN (1 mL) was stirred at 80 °C and monitored by TLC. After completion of the reaction, the mixture was purified by flash chromatography. |
| 83% |
With bismuth(lll) trifluoromethanesulfonate In acetonitrile for 10h; Reflux; |
15 A typical method for preparation of a nitrile from an aldoxime using Bi(OTf)3 as the catalyst:
4-Isopropylbenzaldoxime 2a (0.5 g, 3 mmol), Bi(OTf)3 (60 mg, 0.09 mmol) and acetonitrile (5 ml) were taken into a 25 ml round bottomed flask fitted with a condenser and CaCl2 guard tube. The mixture was refluxed and when reaction was complete (GC), the reaction mixture was cooled to room temperature, concentrated under reduced pressure and the crude product was purified by normal column chromatography (silica gel 100-200 mesh, EtOAc/hexane = 1:20) to obtain 4-isopropylbenzonitrile 3a (0.43 g, 97%), which gave the spectral data identical to that given above. |
| 81% |
With 1,1'-oxalyldiimidazole In benzene 15 min, r.t; 65-70 degC, 60 min; |
|
| 80% |
With cerium(IV) oxide In o-xylene at 160℃; for 6h; Dean-Stark; Inert atmosphere; |
|
| 77% |
With 2,2'-oxalyldi(o-sulfobenzimide) In acetonitrile 1) r.t., 15 min, 2) reflux, 90 min; |
|
| 76% |
With (E)-ethyl 2-cyano-2-(2-nitrophenylsulfonyloxyimino)acetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 20℃; Inert atmosphere; |
Representative procedure for nitrile synthesis
General procedure: In an oven-dried two-necked 50 mLround-bottomed flask, equipped with a stirring bar, a solution of the oxime(1.0 mmol) and 2-NO2-C6H4-SO3XY(1.5 mmol) dissolved in anhydrous CH2Cl2 (5.0 mL) wasplaced under the atmosphere of nitrogen. The reaction mixture was stirred atroom temperature for 5 min, then DBU (2.5 mmol) was added drop wise over 2 min.The reaction mixture became a clear homogeneous solution after addition of DBU.The reaction was monitored by TLC. The reaction mixture was diluted with EtOAcand washed with water (2×5 mL) followed by brine (2×5 mL) upon completeconsumption of the starting material. Product was purified by columnchromatography.Furthermore, the by-product Oxymacould be readily recovered by acidifying the aqueous layer, and then extractingwith ethyl acetate. The Oxyma thus recovered can then be reused to regeneratethe sulfonate ester of Oxyma, which can be further used for a separate batch ofreaction. |
| 71% |
With sodium chloride In methanol Ambient temperature; platinum electrodes, electrolysis at constant current; |
|
| 68% |
With trifluoromethylsulfonic anhydride; triethylamine In tetrahydrofuran at 0℃; for 1.5h; |
General procedure for dehydration of aldoximesinto nitriles.
General procedure: Triethylamine (3.0 mmol) was added to a stirred mixture of aldoxime (1.5 mmol) and 10 mL of THF, and trifluoromethanesulfonic anhydride (3.0 mmol) was then added. The mixture was stirred at 0 °C for a time indicated in Table 1, and the progress of the reaction was monitored by TLC (ethyl acetate-hexane, 6:1). After completion of the reaction, the mixture was poured into water, neutralized with a 10% solution of NaHCO3 (20 mL), and extracted with ethylacetate (3×10 mL). The combined extracts were dried over anhydrous Na2SO4 and concentrated, and the residue was purified by column chromatography on silica gel (60-120 mesh) using ethyl acetate-petroleum ether (2:1) as eluent. |
| 61% |
With copper diacetate In acetonitrile at 20℃; for 3h; Ultrasound irradiation; |
|
| 96 %Chromat. |
With 1,3,5-trichloro-2,4,6-triazine; C2F6NO4S2(1-)*C8H14N3O(1+) In acetonitrile at 20℃; for 3h; |
|
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