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CAS No. : | 33797-51-2 | MDL No. : | MFCD00011810 |
Formula : | C3H8IN | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | VVDUZZGYBOWDSQ-UHFFFAOYSA-M |
M.W : | 185.01 | Pubchem ID : | 2724133 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | In diethyl ether for 5h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
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In [D3]acetonitrile at 65℃; |
Yield | Reaction Conditions | Operation in experiment |
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75% | With potassium carbonate In dichloromethane | |
70% | With potassium carbonate In dichloromethane for 16h; Reflux; | 5.1.1.58. 5-[3-(N,N-dimethylaminomethyl)-4-hydroxybenzylidene]-3-(4-methoxyphenyl)-1,3-oxazolidin-2,4-dione (12c) To a mixture of p-hydroxybenzaldehyde (1.0 g, 8.2 mmol), N,N-dimethylmethylene ammonium iodide (1.6 g, 1.0 equiv) in dichloromethane (30 mL) was added anhydrous potassium carbonate (1.7 g, 1.5 equiv). The mixture was stirred under reflux for 16 h. After cooling, the mixture was extracted with chloroform, and the organic layers was washed with brine and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed in vacuo, and the residue was purified by silica gel column chromatography, eluted with chloroform/methanol (v/v = 30/1) to give 3-(N,N-dimethylaminomethyl)-4-hydroxybenzaldehyde (1.0 g, 70%); 1H NMR (400 MHz, CDCl3) δ 2.37 (s, 6H), 3.73 (s, 2H), 6.91 (d, J = 8.3 Hz, 1H), 7.54-7.55 (m, 1H), 7.70 (dd, J = 2.1, 8.3 Hz, 1H), 8.00-9.50 (brs, 1H), 9.81 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | In tetrahydrofuran at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
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82% | In dichloromethane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
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45% | In tetrahydrofuran for 24h; Heating / reflux; | INTERMEDIATE 13; 3-r(Dimethylamino)methyl1-6-iodoimidazo[l,2-(a;]pyridine; A stirred solution of 6-iodoimidazo[l,2-α]pyridine (2.0 g, 8.2 mmol) and Eschenmoser's salt (5.0 g, 2.7 mmol) in THF (50 mL) was heated to reflux for 24 h. The reaction mixture was then diluted with EtOAc (50 mL), washed with water (3 x 20 mL), dried (MgSO4), filtered and concentrated in vacuo. The residual solid was triturated from Et2O, collected by filtration and dried to give the title compound (1.1 g, 45%) as a brown powder. δH (DMSO-d6) 8.67 (IH, m), 7.45 (IH, s), 7.43-7.41 (2H, m), 3.72 (2H, s), 2.14 (6H, s). LCMS (ES+) 302.2 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: 4-hydroxy-N N,2-trimethyl-1-[(4-methylphenyl)sulfonyl]-1H-benzimidazole-6-carboxamide; eschenmoser's salt In dichloromethane at 20 - 40℃; for 15h; Stage #2: With sodium hydrogencarbonate In dichloromethane; water | 8.5 To a solution of 4-hydroxy-λ/,λ/,2-trimethyl-1-[(4-methylphenyl)sulfonyl]-1 H-benzimidazole-6-25 carboxamide (1.00 g, 2.68 mmol, Step 4) in dichloromethane (50 mL) was added/V,λ/-dimethylmethyleneiminium iodide (545 mg, 2.95 mmol) at room temperature and the mixture was stirred at 4O0C for 15 hours. The reaction was quenched by saturated sodium hydrogencarbonate aqueous solution. The mixture was extracted with dichloromethane. The organic layer was dried over sodium sulfate and concentrated in vacuo to afford the title compound as a yellow amorphous (1.04 g,30 90%).1H NMR (CDCI3, 270 MHz) δ: 7.78 (d, J = 8.6 Hz, 2H), 7.35 (s, 1 H), 7.32-7.24 (m, 2H), 3.83-3.56 (br, 2H),3.17 (s, 3H), 2.87 (s, 3H), 2.77 (s, 3H), 2.40 (s, 3H), 2.36 (s, 6H) ppm. (OH was not observed)MS (ESI) m/z: 431 (M+H)+, 429 (M-H)". |
90% | Stage #1: 4-hydroxy-N N,2-trimethyl-1-[(4-methylphenyl)sulfonyl]-1H-benzimidazole-6-carboxamide; eschenmoser's salt In dichloromethane at 40℃; for 15h; Stage #2: With sodium hydrogencarbonate In dichloromethane; water at 20℃; | 1.6 4-hydroxy-λ/,λ/,2-trimethyl-1-[(4-methylphenyl)sulfonyl]-1 /-/-benzimidazole-6- carboxamide (15 g, 40 mmol, STEP 5) and λ/,λ/-dimethylmethyleneiminium iodide (8.9 g, 48 mmol) in dichloromethane (200 ml_) was stirred at 40 0C for 15 hours. The reaction mixture was cooled to room temperature, and quenched with saturated sodium hydrogen carbonate aqueous solution (200 ml_). The mixture was extracted with dichloromethane (200 ml_ x 2). The combined organic layer was dried over magnesium sulfate and concentrated in vacuum. The residue was purified by column chromatography on amino gel (hexane : ethyl acetate gradient elution from 1 : 1 to ethyl acetate only) to afford the title compound as a white amorphous (15.5 g, 90%). 1H NMR (CDCI3, 270 MHz) δ: 7.79-7.76 (d, J = 8.1 Hz, 2H), 7.35-7.30 (m, 3H), 3.90-3.50 (br. s, 2H), 3.17 (s, 3H), 2.86 (s, 3H), 2.77 (s, 3H), 2.40 (s, 3H), 2.35 (s, 6H) ppm (-OH was not observed). MS (ESI) m/z: 431 (M+H)+, 429 (M-H)". |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydrogencarbonate; sodium thiosulfate; In dichloromethane; acetonitrile; | REFERENCE EXAMPLE 20 3-Dimethylaminomethyl-<strong>[177485-39-1]5-ethoxycarbonylimidazo[1,2-a]pyridine</strong> To a solution of 1.90 g (10.0 mmol) of <strong>[177485-39-1]5-ethoxycarbonylimidazo[1,2-a]pyridine</strong> in 40 ml of acetonitrile was added 2.41 g (13.0 mmol) of N,N-dimethylmethyleneammonium iodide. The mixture was heated for two hours under reflux. The solvent was distilled off. To the residue was added methylene chloride. The mixture was washed with an aqueous solution of sodium thiosulfate and an aqueous solution of sodium hydrogencarbonate, successively, dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: ethyl acetate) to afford 1.496 g of the desired compound (60.6%, a pale yellow solid). This product was recrystallized from ethyl acetate to afford the desired compound (colorless crystals), m.p.117.0-118.0 C. Elemental Analysis Calcd for C13 H17 N3 O2: Calcd.: C, 63.14; H, 6.93; N, 16.99 Found: C, 63.09; H, 6.68; N, 16.94 NMR(200 MHz,CDCl3)delta: 1.45(3H,t,J=7.2 Hz), 1.96(6H,s), 3.72(2H,s), 4.45(2H,q,J=7.2 Hz), 7.20(1H,dd,J=8.8, 7.0 Hz), 7.28(1H,dd,J=7.0, 1.6 Hz), 7.59(1H,s), 7.78(1H,dd,J=8.8, 1.6 Hz). IR(KBr): 1718, 1714, 1626. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium cyanide; sodium hydrogencarbonate; methyl iodide In methanol; dichloromethane; water; N,N-dimethyl-formamide | 5-Methoxy-3-indoleacetonitrile (5c). 5-Methoxy-3-indoleacetonitrile (5c). A solution of N,N-dimethylmethylene ammonium iodide (3.25 g, 17.5 mmol) and 5-methoxyindole, 5a (1.47 g, 10 mmol) in CH2 Cl2 (100 mL) was stirred at room temperature for 6 hours with exclusion of moisture. A saturated aqueous solution of NaHCO3 was added to the ice-cooled reaction mixture with stirring. The layers were separated, the organic phase was washed with water, dried (Na2 SO4) and evaporated in vacuo. The crude 5b was dissolved in methanol (50 mL); 2.5 mL of DMF and 2.5 mL of water were added, followed by KCN (5.2 g, 80 mmol) and MeI (14.2 g, 100 mmol). The reaction mixture was warmed at 50° C. for 3 hours, then it was poured into ice-water and extracted with CH2 Cl2. The extracts were washed with brine, dried (Na2 SO4) and concentrated in vacuo. The residue was re-crystalized from ethyl acetate-hexane (1.02 g, yield: 55%, starting from 5a), oil. 1 H NMR: 3.71(s, 2H, CH2), 3.88(s, 3H, OCH3), 6.97-7.73(m, 4Harom), 8.41(br s, 1H, NHindole). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With acetic acid at 125℃; for 1h; | 92.1 Step 1 1-(4-Chloro-phenyl)-propan-2-one (8.6 g, 51 mmol) and Eschenmoser's salt (12.3 g, 66.3 mmol) were dissolved in glacial acetic acid and heated in a closed pressure tube at 125° C. under nitrogen for 1 h. After cooling to room temperature, the solution was concentrated. The residue was dissolved in EtOAc, washed with saturated NaHCO3 aqueous solution, dried (MgSO4), concentrated, and chromatographed (SiO2, 39:1-19:1 hexane/EtOAc) to give 3-(4-chloro-phenyl)-but-3-en-2-one as yellow oil (3.92 g, 43%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | Preparation of 1 , 2-bis- (dimethylaminomethyl) ferrocenen-Butyllithium (Aldrich, 2.5 molar in hexane, 24 ml, 54 mmol) is added to a solution of (dimethylaminomethyl ) ferrocene (Aldrich, 13.13 g, 10.69 ml, 48.97 mmol) in diethyl ether (80 ml) under nitrogen at a temperature of 25C and the reaction mixture stirred for 4 hours. The resulting red solution is then cooled to approximately -700C in a dry ice/acetone bath and Eschenmosers salt (ICH2NMe2) (Aldrich, 10 g, 54 mmol) is added. The reaction is allowed to warm to room temperature and stirred overnight .The resultant solution is quenched with excess aqueous sodium hydroxide and the resulting product extracted with diethyl ether (3 x 80 ml) dried over anhydrous magnesium sulfate, filtered over celite, and volatiles removed in vacuo to yield the crude title compound as a light orange crystalline solid. The crude product is recrystallised from light petrol with cooling to -17C and the recrystallised product washed with cold petrol to yield the title compound as a light orange solid (13.2 g, 74%). The compound can be further purified by sublimation to give 8.5 g (52%) of the Part (I) title compound (mpt 74C) .1H NMR(250 MHz; CDCl3 ) : 54.23 (brd, 2H) ; 4.11-4.10 (t, IH) ; 4.04(s, 5H) ; 3.43, 3.38, 3.23, 3.18 (AB quartet, 2H) ; 2.22(s, 6H) . <n="94"/>13C NMR (63 MHz; CDCl3 ): 583.81 ; 70.40; 69.25; 66.84; 57.35; 45.23.Elemental analysis: Found: C 63.7%; H 8.9%; N 9.5% Calculated: C 64.0%; H 8.1%; N 9.4% | |
52% | n-Butyllithium (Aldrich, 2.5 molar in 82 hexane, 24 ml, 54 mmol) is added to a solution of 83 <strong>[1271-86-9](dimethylaminomethyl)ferrocene</strong> (Aldrich, 13.13 g, 10.69 ml, 48.97 mmol) in 31 diethyl ether (80 ml) under nitrogen at a temperature of 25 C. and the reaction mixture stirred for 4 hours. The resulting red solution is then cooled to approximately -70 C. in a dry ice/acetone bath and Eschenmosers salt (ICH2NMe2) (Aldrich, 10 g, 54 mmol) is added. The reaction is allowed to warm to room temperature and stirred overnight. (0510) The resultant solution is quenched with excess aqueous sodium hydroxide and the resulting product extracted with diethyl ether (3×80 ml) dried over anhydrous magnesium sulfate, filtered over celite, and volatiles removed in vacuo to yield the crude title compound as a light orange crystalline solid. The crude product is recrystallised from light petrol with cooling to -17 C. and the recrystallised product washed with cold petrol to yield the 84 title compound as a light orange solid (13.2 g, 74%). The compound can be further purified by sublimation to give 8.5 g (52%) of the title compound (mpt 74 C.). (0511) 1H NMR (250 MHz; CDCl3): δ4.23 (brd, 2H); 4.11-4.10 (t, 1H); 4.04 (s, 5H); 3.43, 3.38, 3.23, 3.18 (AB quartet, 2H); 2.22 (s, 6H). (0512) 13C NMR (63 MHz; CDCl3): δ83.81; 70.40; 69.25; 66.84; 57.35; 45.23. (0513) Elemental analysis: Found: C, 63.7%; H, 8.9%; N, 9.5%. (0514) Calculated: C, 64.0%; H, 8.1%; N, 9.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | In dichloromethane; at 20℃; | To a solution of 3-nitropropionic acid (1.Og, 8.4mmol) and triazole base 1 (2.4g, 10.5mmol) in acetonitrile (2OmL) at O0C was added N-methylmorpholine (0.92mL,8.4mmol), followed by l-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride(2.42g, 12.6mmol) and the reaction mixture stirred for Ih. The reaction mixture was allowed to self warm to room temperature and stirred overnight. The reaction mixture was diluted with ethyl acetate and washed with water, sat. NaHCO3(aq), and brine. The organic phase was dried over MgSO4, evaporated and the residue triturated with diethyl ether to give amide 9 (2.1g, 85percent) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile at 80℃; |
Yield | Reaction Conditions | Operation in experiment |
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Example 2; 10-hydroxy-camptothecin (0.1 g) , N,N-dimethylmethyleneiminium iodide (about 0.06 g) , dichloromethane (about 1.3 g) , and isopropanol (about 0.8 g) were charged into a suitable reactor. The resulting mixture was stirred for 5-10 minutes. Then triethylamine (0.002-0.03 g) was added, and the resulting mixture was stirred at room temperature . After the reaction was complete, the mixture of hydrochloride acid (37%, 0.003-0.045 g) and isopropanol (about 0.14 g) was added to the resulting mixture. The resulting mixture was stirred over 4 hours, and then the solid was filtered, washed with dichloromethane <n="9"/>(about 1 g) and dried under vacuum to give about 0.11 g of topotecan HCl . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.16 g | In methanol at 23 - 65℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methanesulfonic acid; sulfuric acid In chloroform-d1 at 20 - 70℃; for 3h; screw-capped test-tube; | Eschenmoser's (iodide) salt was employed as a commercially available iminium salt. When this salt was mixed into deuterated chloroform, the salt was observed to be scarcely soluble at room temperature. However, when MeSO3H and H2SO4 were added, the colour changed becoming dark brown and the solubility increased. After heating in the presence of added ethyl cyanoacetate on an equimolar basis at a temperature of 70° C. for a period of time of 3 hours, the reaction produced monomeric cyanoacrylate, as evidenced by direct 1N NMR analysis. | |
Stage #1: eschenmoser's salt With methanesulfonic acid; sulfuric acid In chloroform-d1 Stage #2: ethyl 2-cyanoacetate In chloroform-d1 at 70℃; for 3h; | For comparative purposes, Eschenmoser's iodide salt-a non-protonated iminium salt-was employed as a commercially available iminium salt, and was placed in deuterated chloroform and observed to be scarcely soluble. When MeSO3H and H2SO4 were added the solubility was observed to increase. After heating in the presence of ethyl cyanoacetate on an equimolar basis at a temperature of 70° C. for a period of time of 3 hours, the reaction produced monomeric cyanoacrylate in low yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: thiophen-3-yl-acetic acid methyl ester With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.5h; Stage #2: eschenmoser's salt In tetrahydrofuran at -78 - 0℃; | 42 Preparation of methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42) Example 42 Preparation of methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42) To methyl 2-(thiophen-3-yl)acetate (E41) in THF cooled to -78° C. was added LiHMDS, and the solution stirred at -78° C. for 30 min. Then N,N-Dimethylmethyleneiminium iodide was added directly and the solution was allowed to warm to 0° C. The mixture was poured into NaHCO3 (sat), extracted with EtOAc, dried (Na2SO4), filtered, and evaporated. Column chromatography (SiO2, 5% MeOH/CH2Cl2) gave pure methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42). | |
Stage #1: thiophen-3-yl-acetic acid methyl ester With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.5h; Stage #2: eschenmoser's salt In tetrahydrofuran at -78 - 0℃; | 42 Example 42. Preparation of methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42). To methyl 2-(thiophen-3-yl)acetate (E41) in THF cooled to -78 °C was added LiHMDS, and the solution stirred at -78 °C for 30 minutes. Then N,N- dimethylmethyleneiminium iodide (Eschenmoser’s salt) was added directly and the solution was allowed to warm to 0 °C. The mixture was poured into NaHC03 (sat. aq.), extracted with EtOAc, dried over Na2S04, filtered, and the solvent evaporated. Column chromatography (Si02, 5% MeOH/CH2Cl2) gave pure methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
lH-Indole-7-carboxylic acid, methyl ester (0.091 mol), Eschenmoser's salt (0.1 mol) in acetic acid (300 ml) were heated at 650C for 2 hours. The precipitate was filtered off, dissolved in DCM and potassium carbonate 10percent. Potassium carbonate (solid) was added and the mixture was stirred at room temperature for 1 hour and then extracted. The organic layer was separated, dried over MgSO4, filtered and the solvent was evaporated, yielding 1Og of intermediate 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | Step 7[00134] 3-[(Dimethylamino)methyl1-5-methylhexan-2-one: To a stirred solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-N- methylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20C overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 Nu HCl (aq.) and extracted with ieri-butyl methyl ether. Then the water phase was basiced with 2 Nu aq. NaOH and extracted with ieri-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80C/0.5 mmHg) to provide 50 g (46%) of 3- [(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. 'H-NMR (300 MHz, -DMSO) 0.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, IH), 1.23-1.38 (m, IH), 1.54-1.70 (m, IH), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.81-3.88 (m, IH). | |
46% | In acetonitrile; at 20℃; | [0199] 3-[(Dimethylamino)methyl]-5-methylhexan-2-one: To a stuffed solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-N-methylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20C overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 N HC1 (aq.) and extracted with tert-butyl methyl ether. Then the water phase was basiced with 2 N aq. NaOH and extracted with tert-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80C/0.5 mmHg) to provide 50 g (46%) of 3-[(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. ?H-NMR (300 MHz, d6-DMSO) cY0.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, 1H), 1.23-1.38 (m, 1H), 1.54-1.70 (m, 1H), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.8 1-3.88 (m, 1H). |
46% | In acetonitrile; at 20℃; | To a stilTed solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-N-methylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20C overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 N HC1 (aq.) and extracted with tert-butyl methyl ether. Then the water phase was basiced with 2 N aq. NaOH and extracted with tert-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80C/0.5 mmHg) to provide 50 g (46%) of 3-[(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. ?H-NMR (300 MHz, d6-DMSO) c50.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, 1H), 1.23-1.38 (m, 1H), 1.54-1.70 (m, 1H), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.81-3.88 (m, 1H). |
46% | In acetonitrile; at 20℃; | To a stirred solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-N-methylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20 C. overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 N HCl (aq.) and extracted with tert-butyl methyl ether. Then the water phase was basiced with 2 N aq. NaOH and extracted with tert-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80 C./0.5 mmHg) to provide 50 g (46%) of 3-[(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. 1H-NMR (300 MHz, d6-DMSO) delta0.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, 1H), 1.23-1.38 (m, 1H), 1.54-1.70 (m, 1H), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.81-3.88 (m, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With triethylamine In dichloromethane Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | Stage #1: 4-bromo[2.2]paracyclophane With n-butyllithium In diethyl ether; hexane at 20℃; for 2h; Inert atmosphere; Stage #2: eschenmoser's salt In diethyl ether; hexane at 20℃; for 1h; Inert atmosphere; Stage #3: With hydrogenchloride In diethyl ether Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydrogencarbonate In N,N-dimethyl-formamide at 125℃; for 0.5h; Microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic acid In methanol at 25℃; for 4h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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55% | Stage #1: ferrocene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In hexane; pentane at 20℃; for 22h; Inert atmosphere; Stage #2: eschenmoser's salt In diethyl ether; hexane; pentane at 20℃; for 18.17h; Reflux; Inert atmosphere; | 5 Synthesis of Fc(NMe2)2 Example 5. Synthesis and Characterization of FcN2 Synthesis of Fc(NMe2)2 The solution of n-BuLi (2.5 M, 7.2 mL, 18.0 mmol) in hexane was added into the mixture of Fc (1.62 g, 8.7 mmol) and TMEDA (2.68 mL, 18.0 mmol) in 80 mL dry pentane. After stirred at room temperature for 4 h, orange precipitate was observed. The dark orange solution was stirred at room temperature for another 18 h, 80 mL of dry ether was added to dilute the reaction mixture. Solid Eschenmoser's salt was added in one portion, the mixture was stirred at room temperature for another 18 h and heated up under reflux for 10 min. 2 mL H2O was added to quench the reaction, and then, the organic phase was washed with 50 mL H2O and 50 mL brine, dried with Na2SO4. The product was purified by flash column chromatography with neutral alumina (ethyl acetate:MeOH=10:1). The pure product was obtained as an orange oil (1.44 g, 55% yield). 1H NMR (CDCl3, 500 MHz, ppm): δ 2.18 (s, 12H), 3.27 (s, 4H), 4.08 (s, 4H), 4.11 (s, 4H). |
35% | Stage #1: ferrocene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In hexane at 20℃; for 13h; Inert atmosphere; Schlenk technique; Stage #2: eschenmoser's salt In tetrahydrofuran at 20℃; for 24h; Reflux; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
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112 mg | In N,N-dimethyl-formamide; acetonitrile at 90℃; | 211.2 Step 21 1.2: To a solution of ethyl 2-(3-methyl-1H-pyrazol-1-yl)acetate (94mg) and DMF (1.5mL) in MeCN (3mL) was added Ν,Ν-dimethylmethyleneiminium iodide (390mg). The reaction mixture was stirred at 90°C overnight. After cooling down, the reaction mixture was diluted with DCM and washed with sat. NaHCO3 and water. The aq. layers were extracted with DCM, the combined org. layers were dried (MgSO4), filtered off and evaporated in vacuo to afford ethyl 2-(4-((dimethylamino)methyl)-3-methyl-1H-pyrazol-1-yl)acetate (112mg, brown oil). LC-MS (B): tR = 0.39min; [M+H]+: 226.23. |
112 mg | In N,N-dimethyl-formamide; acetonitrile at 90℃; | 211.2 Step 211.2: To a solution of ethyl 2-(3-methyl-1H-pyrazol-1-yl)acetate (94 mg) and DMF (1.5 mL) in MeCN (3 mL) was added N,N-dimethylmethyleneiminium iodide (390 mg). The reaction mixture was stirred at 90° C. overnight. After cooling down, the reaction mixture was diluted with DCM and washed with sat. NaHCO3 and water. The aq. layers were extracted with DCM, the combined org. layers were dried (MgSO4), filtered off and evaporated in vacuo to afford ethyl 2-(4-((dimethylamino)methyl)-3-methyl-1H-pyrazol-1-yl)acetate (112 mg, brown oil). LC-MS (B): tR=0.39 min; [M+H]+: 226.23. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | Stage #1: l-triptonide With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: eschenmoser's salt In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | In acetonitrile; at 60℃; | General procedure: A sample of the heterocycle was dissolvedin CH2Cl2 or CH3CN (as shown in Tables 1 and 2, 0.15?0.2 M).Dimethylmethylideneammonium iodide (Eschenmoser?s salt, 2 equiv.) was added in a singleportion. The reaction mixture was stirred at room temperature or at 60 °C until TLC analysisindicated the complete consumption of the starting material (20 min?26 h). The reactionmixture was diluted with CH2Cl2 or EtOAc (for CH3CN as reaction medium) and saturatedaqueous NaHCO3. The phases were separated, and the aqueous layer was extracted once. TheS3organic layer was dried (Na2SO4), and the solvent was evaporated. The crude product wasused without further purification in the next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | In acetonitrile; at 20℃; | 3- j(Dimethylamino)methyll-5-methylhexan-2-one: To a stirred solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-Nmethylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20C overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 N HC1 (aq.) and extracted with tert-butyl methyl ether. Then the water phase was basiced with 2 N aq. NaOH and extracted with tert-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80C/0.5 mmHg) to provide 50 g (46%) of 3- [(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. ?H-NMR (300 MHz, d6-DMSO) NO.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, 1H), 1.23-1.38 (m, 1H), 1.54-1.70 (m, 1H), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.81-3.88 (m, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87.5% | Under a nitrogen atmosphere,2.0370 g (5.924 mmol) of <strong>[1293-65-8]1,1'-<strong>[1293-65-8]dibromoferrocene</strong></strong> was dissolved in THF (50 ml)Under cooling at -78 C.,4.0 ml (6.516 mmol) of n-butyllithium (1.6 M, n-hexane solution) was added and the mixture was stirred for 20 minutes.ThenN, N-dimethylmethylene ammonium iodide2.2 g (11.848 mmol) was added, then the mixture was allowed to stand at room temperature and stirred for 16 hours.An ammonium chloride aqueous solution (100 ml) and chloroform (150 ml) were added to the reaction solution, and the mixture was separated. The aqueous phase was further extracted twice with 50 ml of chloroform.The obtained organic phase (250 ml) was washed with saturated brine,After drying over sodium sulfate, concentration under reduced pressure gave a crude product. This was purified by silica gel column chromatography to obtain 1.6692 g (5.1835 mmol, yield 87.5%) of 1-bromo-1 '- ((dimethylamino) methyl) ferrocene as an intermediate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With n-butyllithium; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 14.5h; | 1.1; 1.1; 2.1; 3.1; 4.1; 5.1; 6.1 (1) Preparation of 2-methylene-4-hydroxybutanal 1.5 L of tetrahydrofuran was added to a 3 L flask, stirring was started, the rotation speed was set to 800 rpm, the temperature was lowered to -10 ° C, and then 3 mol of n-butyllithium and 2.5 mol of diisopropylamine were added thereto.After 2.5 hours of reaction,Add 1 mol of 4-hydroxybutanal and stir for 2.5 h.1.5 mol of (N,N-dimethyl)methylene iodide was added, followed by reaction at room temperature for 12 h.At the end of the reaction, 0.5 L of water was added to the system, and the mixture was extracted three times with dichloromethane, 0.5 L each time. The organic phase was combined, and dichloromethane was recovered under reduced pressure. The mother liquid was distilled off at 1 kPa with a packed column of theoretical number of 20 The reaction solution after removing the solvent,The reflux ratio was 2:1, and the fraction at the top of the column was collected at 38-39 ° C.Obtaining 2-methylene-4-hydroxybutanal,The content of 2-methylene-4-hydroxybutanal was analyzed by gas chromatography to be 97.2%, and the yield was 96%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Step 1: using 5-methyl-3-hexen-2-one (1 mol) and tetramethyldisiloxane (0.8 mol) as raw materials.The addition reaction is carried out under the condition of a copper hydride triphenylphosphine complex (0.8% mol) as a catalyst.The reaction solvent is 1.5 L of toluene, the reaction temperature is 90 C, and the reaction time is 2 hours to obtain Intermediate 6;Step 2: Adding N,N-dimethylmethylene iodide (1.5 mol) to the intermediate 6 obtained in the first stepAnd an anhydrous zinc chloride (5% mol) catalyst to carry out Mannich reaction,The reaction temperature is 90 C, and the reaction time is 3 hours.That is, a crude 3-[(dimethylamino)methyl]-5-methyl-2-hexanone is obtained;Step 3: Purifying the crude 3-[(dimethylamino)methyl]-5-methyl-2-hexanone obtained in the second step by distillation,That is, 3-[(dimethylamino)methyl]-5-methyl-2-hexanone is obtained as a fine product.The final product was 115g;The purity of the final 3-[(dimethylamino)methyl]-5-methyl-2-hexanone was 99.6%, and the yield was 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With triethylamine In dichloromethane at 40℃; for 48h; |
Tags: 33797-51-2 synthesis path| 33797-51-2 SDS| 33797-51-2 COA| 33797-51-2 purity| 33797-51-2 application| 33797-51-2 NMR| 33797-51-2 COA| 33797-51-2 structure
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