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CAS No. : | 504-20-1 | MDL No. : | MFCD00008901 |
Formula : | C9H14O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MTZWHHIREPJPTG-UHFFFAOYSA-N |
M.W : | 138.21 | Pubchem ID : | 10438 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.44 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 44.63 |
TPSA : | 17.07 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.13 cm/s |
Log Po/w (iLOGP) : | 2.32 |
Log Po/w (XLOGP3) : | 2.84 |
Log Po/w (WLOGP) : | 2.49 |
Log Po/w (MLOGP) : | 2.19 |
Log Po/w (SILICOS-IT) : | 2.06 |
Consensus Log Po/w : | 2.38 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.35 |
Solubility : | 0.612 mg/ml ; 0.00443 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.86 |
Solubility : | 0.192 mg/ml ; 0.00139 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -1.53 |
Solubility : | 4.1 mg/ml ; 0.0296 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.48 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | 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 |
---|---|---|
71% | With ammonia; acetic acid In methanol | EXAMPLE 3 100 ml of methanol, 150 ml of liquid ammonia, 1 ml of acetic acid and 20 g of a standard commercial hydrogenation catalyst (Raney cobalt), were introduced into a 0.7 litre capacity hydrogenation autoclave. The autoclave was heated to the hydrogenation temperature of approximately 150°C under a hydrogen pressure of approximately 100 atms, after which a solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of about 1 hour. Hydrogenation was complete after about another hour. After cooling, the autoclave was vented, the reaction solution filtered off from the catalyst and subjected to fractional distillation, yielding 80 g (71percent of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 82°-88°C/15 Torr. |
64% | With acetic acid In methanol | EXAMPLE 1 100 ml of methanol, 150 ml (approximately 6 moles) of liquid ammonia and 1 ml of acetic acid, together with 20 g of a standard hydrogenation catalyst (Raney cobalt), were introduced into a 0.7 litre capacity hydrogenation autoclave. The autoclave was then heated to a temperature of approximately 110°C and the hydrogen pressure maintained in the range from 130 to 150 atms. After the prescribed hydrogenation temperature of 110°C had been reached, a solution of 100 g (0.725 mol) of phorone in 100 ml of methanol was pumped in over a period of 1 hour. Hydrogenation was over after about another hour. After cooling, the autoclave was vented, the reaction solution filtered off from the catalyst and subjected to fractional distillation, yielding 72.5 g (64percent of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 88°-92°C/16 Torr. |
54% | With ammonia; acetic acid In methanol | EXAMPLE 2 100 ml of methanol, 150 ml of liquid ammonia, 1 ml of acetic acid and 20 g of a standard commercial hydrogenation catalyst (Raney nickel) were introduced into a 0.7 litre capacity autoclave. The autoclave was heated to a hydrogenation temperature of 110°C under a hydrogen pressure of 130 to 150 atms, after which a solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of approximately 1 hour. Hydrogenation was over after about another hour. After cooling, the autoclave was vented, the reaction solution filtered off from the catalyst and subjected to fractional distillation, yielding 61 g (54percent of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 89°-95°C/18 Torr. |
41.5% | With ammonia; acetic acid In methanol | EXAMPLE 6 100 ml of methanol, 110 ml of liquid ammonia, 1 ml of acetic acid and 20 g of a standard commercial hydrogenation catalyst (Raney cobalt) were introduced into a 0.7 litre capacity hydrogenation autoclave, after which the autoclave was heated to approximately 80°C under a hydrogen pressure of approximately 100 atms. The hydrogen pressure was then increased to 250 atms, and a solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of about 1 hour, during which the hydrogen pressure was kept between 225 and 250 atms. Hydrogenation was over after about 20 minutes. The reaction solution was then filtered off from the catalyst and subjected to fractional distillation, yielding 47 g (41.5percent of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 80° to 91°C/16-18 Torr. |
38% | With acetic acid In methanol | EXAMPLE 4 100 ml of methanol, 110 ml (approximately 4 moles) of liquid ammonia, 1 ml of acetic acid and 15 g of standard commercial hydrogenation catalyst (Raney cobalt) were introduced into a 0.7 litre capacity hydrogenation autoclave. The autoclave was heated to 80°C under a hydrogen pressure of about 80 to 100 atms, after which the hydrogen pressure was kept at around 180 atms. A solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of about 1 hour. Hydrogenation was over after about 45 minutes. After cooling, the autoclave was vented, the reaction solution was filtered off from the catalyst and subjected to fractional distillation, yielding 43 g (38percent of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 82°-92°C/15-16 Torr. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65.5% | With ammonia; acetic acid In methanol | EXAMPLE 7 100 ml of methanol, 150 ml of liquid ammonia, 1 ml of acetic acid and 15 g of Raney cobalt were introduced into a 0.7 litre capacity hydrogenation autoclave. The autoclave was heated to approximately 180°C under a hydrogen pressure of 80 to 100 atms, after which a solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of 1 hour. After about 30 minutes, the fall in pressure and, hence, hydrogenation was over. After cooling, the autoclave was vented and the reaction solution filtered off from the catalyst and subjected to fractional distillation, yielding 74 g (65.5percent of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 90° to 93°C/18 Torr. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With hydrogenchloride In water at 40℃; for 48 h; | 5 g of commercial phorone are dissolved in 36 ml of a IM solution of hydrochloric acid and heated at 40°C for 2 days. The reaction mixture is distilled (63-65°C) so as to give 3.0 g of a yellowish oil. Yield = 53percent.1H NMR (DMSO D6, 400 MHz) : 1.25 (m, 4H); 2.3 (m, 12H) . |
25% | With hydrogenchloride In water at 45℃; for 168 h; | Step 1. 2,2,6,64etramethyIdihydro-2H-pyran4(3H)-one: To a stirred solution of 2,6 diniethyihepta-2.5--dien-4one (100 g, 0.724 mol) was added 6N HC1 (600 mL). then the reaction mixture was heated to 45 °C for 7 days, Upon completion, the reaction was quenched with ice cold water and extracted with ethyl acetate (4 x 1 50 mL). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered, andconcentrated under reduced pressure to provide a residue. Purification by column chromatography on silica gel (i00200 mesh) using ethyl acetate in hexanc afforded the title compound as a yellow liquid. (yield 28 g, 25percent) |
25% | at 45℃; for 168 h; | Step 1. 2,2,6,6-tetramethyldihydro-2H-pyran-4(3H)-one To a stirred solution of 2,6-dimethylhepta-2,5-dien-4-one (100 g, 0.724 mol) was added 6N HCl (600 mL), then the reaction mixture was heated to 45° C. for 7 days. Upon completion, the reaction was quenched with ice cold water and extracted with ethyl acetate (4*150 mL). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to provide a residue. Purification by column chromatography on silica gel (100-200 mesh) using ethyl acetate in hexane afforded the title compound as a yellow liquid. (yield 28 g, 25percent) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With diethyl ether | ||
In diethyl ether |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With ammonium hydroxide at -80 - 85℃; | |
With ammonia; water | ||
With ammonia |
With ammonium hydroxide; sodium hydroxide 1.) 25 deg C, 3 days, 80 deg C, 60 min; 2.) 0-5 deg C; Yield given. Multistep reaction; | ||
With ammonium hydroxide In water at 55 - 85℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With hydrogenchloride; In water; at 40℃; for 48h; | 5 g of commercial phorone are dissolved in 36 ml of a IM solution of hydrochloric acid and heated at 40C for 2 days. The reaction mixture is distilled (63-65C) so as to give 3.0 g of a yellowish oil. Yield = 53%.1H NMR (DMSO D6, 400 MHz) : 1.25 (m, 4H); 2.3 (m, 12H) . |
25% | With hydrogenchloride; In water; at 45℃; for 168h; | Step 1. 2,2,6,64etramethyIdihydro-2H-pyran4(3H)-one: To a stirred solution of 2,6 diniethyihepta-2.5--dien-4one (100 g, 0.724 mol) was added 6N HC1 (600 mL). then the reaction mixture was heated to 45 C for 7 days, Upon completion, the reaction was quenched with ice cold water and extracted with ethyl acetate (4 x 1 50 mL). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered, andconcentrated under reduced pressure to provide a residue. Purification by column chromatography on silica gel (i00200 mesh) using ethyl acetate in hexanc afforded the title compound as a yellow liquid. (yield 28 g, 25%) |
25% | With hydrogenchloride; water; at 45℃; for 168h; | Step 1. 2,2,6,6-tetramethyldihydro-2H-pyran-4(3H)-one To a stirred solution of 2,6-dimethylhepta-2,5-dien-4-one (100 g, 0.724 mol) was added 6N HCl (600 mL), then the reaction mixture was heated to 45 C. for 7 days. Upon completion, the reaction was quenched with ice cold water and extracted with ethyl acetate (4*150 mL). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to provide a residue. Purification by column chromatography on silica gel (100-200 mesh) using ethyl acetate in hexane afforded the title compound as a yellow liquid. (yield 28 g, 25%) |
With hydrogenchloride; In water; at 40℃; for 168h; | Phorone (9.967 g, 72.1 mmole) was suspended in 1 N aqueous hydrochloric acid (100 mL). The mixture was heated to 40 C for 7 days, then was cooled to RT. The mixture was extracted with ether (3 x 25 mL). The organics were dried (MGS04) and concentrated. The residue was purified by silica gel chromatography (ISCO SG100C, RediSep 120 g cartridge, 5% EtOAc: hexanes for 5 min, 5% to 15% EtOAc: hexanes over 10 min, 15% EtOAc for 5 min, 15% to 25% EtOAc: hexanes over 10 min, 25% EtOAc: hexanes for 5 min) to provide 52 (2.80 g, 25%) as a pale yellow liquid.'H NMR (CDCI3) : 8 2.43 (s, 4H), 1.32 (s, 12H). | |
With hydrogenchloride; water; at 40℃; for 168h; | (a) 2,2,6,6-Tetramethyloxan-4-one (C4) Phorone (C3)(ABCR, CAS: 504-20-1 , CAT: AB141943) (9.967 g, 72.1 mmol) was suspended in 1 N HCI (100 mL). The mixture was heated at 40C for 7 days then washed with diethyl ether (3 x 50 mL). The organic layers were combined and dried (Na2S04) filtered and the solvent removed to give a yellow oil. The oil was subjected to purification by chromatography (silica, 80%, ethyl acetate/hexane; 20/80, 13 x 100 mm tubes). The product was visualized by PMA stain. Fractions 3-16 were collected to give a pale, yellow oil (4.6825 g, 42%, contains minor impurities but was used in the next step without further purification). H NMR (500 MHz, CDCI3) delta 2.39 (brs, 4H, 2 x CH20), 1.28 (brs, 12H, 4 x CH3). 3C NMR (125 MHz, CDCI3) delta 208.61 , CO; 75.08, C2 and C6; 51.64, C3 and C5, 31.47, 4 x CH3. | |
With hydrogenchloride; In water; at 40℃; for 144h; | Intermediate 2: 2,2,6,6-tetramethyltetrahydro-4H-pyran-4-one Phorone or 2,6-dimethyl-2,5-heptadien-4-one (1 eq) is mixed with an aqueous 1 M HCl solution and the obtained emulsion is stirred at 40 C. for 6 days. The water phase is extracted with DCM, and the organic phase is concentrated and purified by distillation to afford the desired product. | |
With hydrogenchloride; water; at 40℃; for 144h; | Phorone or 2,6-dimethyl-2,5-heptadien-4-one (1 eq) is mixed with an aqueous 1 M HCI solution and the obtained emulsion is stirred at 40C for 6 days. The water phase is extracted with DCM, and the organic phase is concentrated and purified by distillation to afford the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; palladium | ||
With aluminium tris(2,6-diphenylphenoxide); n-butyllithium; diisobutylaluminium hydride 1) toluene, -78 deg C; 2) toluene, THF, hexane, -78 deg C, 15 min; Yield given. Multistep reaction; | ||
With hydrogen In methanol for 16h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With ethanol; lithium In tetrahydrofuran at 20℃; for 12h; | |
90% | With triethylsilane; ethanol for 6h; Heating; | |
88% | With formic acid at 100℃; for 1.2h; |
With ethanol; nickel; platinum Hydrogenation; | ||
With ethanol; hydrogen; palladium | ||
With diethyl ether; hydrogen; platinum | ||
With copper at 160 - 170℃; Hydrogenation; | ||
With hydrogen; nickel at 160 - 225℃; | ||
With nickel at 160 - 170℃; Hydrogenation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With bromine In tetrachloromethane for 0.5h; Ambient temperature; | |
With carbon disulfide; bromine |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrazine hydrate durch Destillation mit KOH und platiniertem Ton; | ||
With ethanol; hydrazine hydrate Erhitzen des Reaktionsprodukts mit Kaliumhydroxid in Gegenwart von Platin/Asbest; | ||
With potassium hydroxide; hydrazine hydrate; platinum 2.) 150 deg C; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; acetic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water | ||
4 Proposed Preparation of 1,4-Dihydro-2,6-dimethyl-4-oxo-1-(1,2,2,6,6-Pentamethyl-4-piperidinyl-3-pyridinecarboxylic acid EXAMPLE 4 Proposed Preparation of 1,4-Dihydro-2,6-dimethyl-4-oxo-1-(1,2,2,6,6-Pentamethyl-4-piperidinyl-3-pyridinecarboxylic acid A sample of 1,2,2,6,6-pentamethyl-4-piperidone is prepared by known procedures from phorone and methyl amine. | ||
4 Proposed Preparation of 1,4-Dihydro-2,6-dimethyl-4-oxo-1-(1,2,2,6,6-Pentamethyl-4-piperidinyl-3-pyridinecarboxylic acid Example 4 Proposed Preparation of 1,4-Dihydro-2,6-dimethyl-4-oxo-1-(1,2,2,6,6-Pentamethyl-4-piperidinyl-3-pyridinecarboxylic acid A sample of 1,2,2,6,6-pentamethyl-4-piperidone is prepared by known procedures from phorone and methyl amine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59.8% | In water at 20℃; for 48h; | |
With water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.5% | at 120℃; for 6h; | |
58% | at 120℃; for 21h; | |
47% | at 150℃; for 15h; Inert atmosphere; |
(i) NaOMe, EtOH, (ii) AcOH; Multistep reaction; | ||
at 115 - 130℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | In neat (no solvent) at 130℃; for 8h; Inert atmosphere; | |
at 115 - 130℃; | ||
at 120 - 140℃; |
at 150℃; for 15h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With aq. (15N)ammonia at -80 - 85℃; | |
86% | With sodium hydroxide; disodium hydrogenphosphate; <SUP>15</SUP>N-ammonium sulfate In benzene at 95℃; for 240h; | |
66% | With sodium hydroxide In benzene at 90℃; for 240h; |
62% | With sodium hydroxide; ammonia at 135℃; for 18h; | |
With sodium hydroxide; disodium hydrogenphosphate; ammonium-<SUP>15</SUP>N hydrochloride In benzene at 95℃; for 240h; | ||
2.7 g | With ammonia monohydrate In water at 55 - 85℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | With lithium aluminium tetrahydride In diethyl ether Ambient temperature; | |
With sodium tetrahydroborate In ethanol Ambient temperature; 2-3 h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With titanium tetrachloride; magnesium; <i>tert</i>-butyl alcohol In tetrahydrofuran for 10h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With calcium hypochlorite; Methamphetamin In dichloromethane; water for 3h; | |
74% | With calcium hypochlorite In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74.5% | With aluminum selenide; sodium acetate In ethanol at 75 - 78℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With hydroxylamine hydrochloride; sodium methylate In methanol for 6h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With hydroxylamine hydrochloride; sodium methylate In methanol for 6h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With potassium hydroxide In water for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 27% 2: 39% | With oxygen at 25℃; for 8h; Irradiation; | |
1: 31% 2: 30% | With air at 25℃; for 3h; Irradiation; | |
1: 12% 2: 30% | With air at 25℃; for 3h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 8% 2: 2% 3: 82% | With titanium tetrachloride; NCNMe2 In benzene at 25℃; | |
With sodium hydroxide In benzene at 40℃; benzyltriethylammonium chloride presence; | ||
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In benzene at 40℃; reaction order, effect of concentration on the initial rate; |
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In benzene at 40℃; effect concentrations, initial rate; | ||
With MgO/ZrO2 mixed oxides at 249.84℃; | Acetone self-condensation General procedure: A 150 mg sample of each catalyst was placed in a 0.4 cm i.d. Ushapedquartz tube located in a PID- controlled furnace. This reactorwas connected to the reaction initial gas flow. The acetone wasinjected by a syringe pump as a liquid in a He flow (0.05 L/min) andvaporized in situ, obtaining a volume concentration of 3.2%. Outgoinggases from the reactor were analyzed online by a ShimadzuGC-2010 gas chromatograph with a FID detector. Before any batch,the catalyst was pretreated in He at 723 K for 1 h. The acetone gas phase condensation was studied in a temperature range from 473to 723 K with steps of 50 K. More details about the reaction proce-dure, the reactor configuration and equipment were described inprevious studies [3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With sodium hydroxide In methanol at 60℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With aluminium tris(2,6-diphenylphenoxide); n-butyllithium; diisobutylaluminium hydride In toluene at -78 - 25℃; for 0.25h; Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With hydrogenchloride In diethyl ether; dichloromethane for 24h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: allyl bromide With indium In tetrahydrofuran for 1.5h; Stage #2: phorone In tetrahydrofuran Stage #3: With hydrogenchloride; oxygen; lithium bromide In tetrahydrofuran; diethyl ether Further stages.; | |
Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With hydroxylamine hydrochloride In pyridine for 72h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With N,N,N,N,N,N-hexamethylphosphoric triamide; lithium diisopropyl amide In tetrahydrofuran; n-heptane; ethylbenzene at -78 - 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N,N,N,N,N,N-hexamethylphosphoric triamide; lithium diisopropyl amide In tetrahydrofuran; n-heptane; ethylbenzene at -78 - 20℃; for 2h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,3-bis-(diphenylphosphino)propane; caesium carbonate; isopropyl alcohol In toluene at 75℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 47% 2: 16% | In acetonitrile at 20℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | Stage #1: Methyltriphenylphosphonium bromide With phenyllithium In diethyl ether; cyclohexane for 0.5h; Stage #2: phorone In diethyl ether; cyclohexane for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | Stage #1: 2,4,4-trimethyl oxazoline With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #3: phorone In tetrahydrofuran; hexane at -78℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With 4 A molecular sieve at 20℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With gallium(III) trichloride In toluene at 100℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With 4 A molecular sieve at 20℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With 4 A molecular sieve at 20℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With N-chloro-succinimide; molecular sieve In acetonitrile at 50℃; for 60h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With N-chloro-succinimide; molecular sieve In acetonitrile at 50℃; for 60h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With N-chloro-succinimide; molecular sieve at 50℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With N-chloro-succinimide at 50℃; for 60h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 1.) NH2NH2*H2O, 2.) KOH/Pt / 2.) 150 deg C 2: phenanthrene / acetonitrile |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 66 percent / 25 °C / in the dark 2: 55 percent / KOH / H2O / 1 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 72.5 percent / 6 h / 120 °C 2: 70.5 percent / S / benzene / 3 h / Heating | ||
Multi-step reaction with 2 steps 1: 115 - 130 °C 2: sulfur / benzene / Heating | ||
Multi-step reaction with 2 steps 1: (i) NaOMe, EtOH, (ii) AcOH 2: sulfur / benzene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 2: 5percent H2SO4 / tetrahydrofuran / 2 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | at 120℃; for 20h; | 1 EXAMPLES; Preparation of Compounds of Formula (I); Example 1 14.6 g (0.106 mol) of 2,6-dimethyl-2,5-heptadien-4-one ('phorone") and 5.0 g (0.053 mol) of 1,2-bisphosphinoethane were brought together in a Schlenk tube and stirred for 20 hours at 120o C. The light yellow solid formed was washed with 2?20 ml of pentane and then dried under reduced pressure to give a white powder. The product was characterized by means of 31P NMR spectroscopy, elemental analysis and GC/MS. Yield: 18.2 g, corresponding to 93% of theory |
93% | at 120℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In carbon disulfide; ethyl acetate; Petroleum ether | 5 EXAMPLE 5 The starting material can be prepared as follows: 47.1 g of bromobenzene and 37.8 g of phorone are stirred at room temperature for 48 hours in the presence of 40 g of aluminum trichloride in 600 ml of carbon disulfide. The reaction mixture is then poured on to ice, extracted with diethyl ether. The extract is washed with water, dried and evaporated. After chromatography on silica gel with petroleum ether (low-boiling) and ethyl acetate (9:1) and recrystallization from hexane, there is obtained 2-bromo-5,6,8,9-tetrahydro-5,5,9,9-tetramethyl-7H-benzocyclohepten-7-one of m.p. 104°-105°. The last-named compound can be reacted further in analogy to Example 1A, paragraph b) to give 6,7,8,9-tetra-hydro-α5,5,9,9-pentamethyl-5H-benzocycloheptene-2-methanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65.5% | With ammonia; acetic acid In methanol | 7 EXAMPLE 7 EXAMPLE 7 100 ml of methanol, 150 ml of liquid ammonia, 1 ml of acetic acid and 15 g of Raney cobalt were introduced into a 0.7 litre capacity hydrogenation autoclave. The autoclave was heated to approximately 180°C under a hydrogen pressure of 80 to 100 atms, after which a solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of 1 hour. After about 30 minutes, the fall in pressure and, hence, hydrogenation was over. After cooling, the autoclave was vented and the reaction solution filtered off from the catalyst and subjected to fractional distillation, yielding 74 g (65.5% of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 90° to 93°C/18 Torr. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With ammonia; acetic acid; In methanol; | EXAMPLE 3 100 ml of methanol, 150 ml of liquid ammonia, 1 ml of acetic acid and 20 g of a standard commercial hydrogenation catalyst (Raney cobalt), were introduced into a 0.7 litre capacity hydrogenation autoclave. The autoclave was heated to the hydrogenation temperature of approximately 150C under a hydrogen pressure of approximately 100 atms, after which a solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of about 1 hour. Hydrogenation was complete after about another hour. After cooling, the autoclave was vented, the reaction solution filtered off from the catalyst and subjected to fractional distillation, yielding 80 g (71% of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 82-88C/15 Torr. |
64% | With acetic acid; In methanol; | EXAMPLE 1 100 ml of methanol, 150 ml (approximately 6 moles) of liquid ammonia and 1 ml of acetic acid, together with 20 g of a standard hydrogenation catalyst (Raney cobalt), were introduced into a 0.7 litre capacity hydrogenation autoclave. The autoclave was then heated to a temperature of approximately 110C and the hydrogen pressure maintained in the range from 130 to 150 atms. After the prescribed hydrogenation temperature of 110C had been reached, a solution of 100 g (0.725 mol) of phorone in 100 ml of methanol was pumped in over a period of 1 hour. Hydrogenation was over after about another hour. After cooling, the autoclave was vented, the reaction solution filtered off from the catalyst and subjected to fractional distillation, yielding 72.5 g (64% of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 88-92C/16 Torr. |
54% | With ammonia; acetic acid; In methanol; | EXAMPLE 2 100 ml of methanol, 150 ml of liquid ammonia, 1 ml of acetic acid and 20 g of a standard commercial hydrogenation catalyst (Raney nickel) were introduced into a 0.7 litre capacity autoclave. The autoclave was heated to a hydrogenation temperature of 110C under a hydrogen pressure of 130 to 150 atms, after which a solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of approximately 1 hour. Hydrogenation was over after about another hour. After cooling, the autoclave was vented, the reaction solution filtered off from the catalyst and subjected to fractional distillation, yielding 61 g (54% of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 89-95C/18 Torr. |
41.5% | With ammonia; acetic acid; In methanol; | EXAMPLE 6 100 ml of methanol, 110 ml of liquid ammonia, 1 ml of acetic acid and 20 g of a standard commercial hydrogenation catalyst (Raney cobalt) were introduced into a 0.7 litre capacity hydrogenation autoclave, after which the autoclave was heated to approximately 80C under a hydrogen pressure of approximately 100 atms. The hydrogen pressure was then increased to 250 atms, and a solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of about 1 hour, during which the hydrogen pressure was kept between 225 and 250 atms. Hydrogenation was over after about 20 minutes. The reaction solution was then filtered off from the catalyst and subjected to fractional distillation, yielding 47 g (41.5% of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 80 to 91C/16-18 Torr. |
38% | With acetic acid; In methanol; | EXAMPLE 4 100 ml of methanol, 110 ml (approximately 4 moles) of liquid ammonia, 1 ml of acetic acid and 15 g of standard commercial hydrogenation catalyst (Raney cobalt) were introduced into a 0.7 litre capacity hydrogenation autoclave. The autoclave was heated to 80C under a hydrogen pressure of about 80 to 100 atms, after which the hydrogen pressure was kept at around 180 atms. A solution of 100 g of phorone in 100 ml of methanol was pumped in over a period of about 1 hour. Hydrogenation was over after about 45 minutes. After cooling, the autoclave was vented, the reaction solution was filtered off from the catalyst and subjected to fractional distillation, yielding 43 g (38% of the theoretical yield) of 4-amino-2,2,6,6-tetramethyl piperidine with a boiling point of 82-92C/15-16 Torr. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With Et2O-HBF4 In ethanol dropwise addn. of phorone to a soln. of 54% Et2O-HBF4 and Fe-compd. at room temp., a suspn. develops after 20 min., pptn. on stirring for 20 h; centrifugating, repeated recrystn. (CH2Cl2/ether), washing 3 times with ether and pentane, drying in vac., elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 20℃; for 48h; Overall yield = 10 %; Overall yield = 0.88 g; | 2,6-Dimethyl-6-methylaminohept-2-en-4-one (8b) To an aqueous solution of 2b (4.3 mL,40%) was added 5 (7.8 mL, 6.90 g, 50 mmol). The mixture was stirred at room temperature for48 h. Thereafter, workup was performed as described for the reaction of 2a with 5. In this case, amixture (2.21 g, 25%) of the products 3b and 8b with an approximate 3:2 ratio was formed.When the workup was conducted with aqueous H2SO4 (15%) instead of aqueous HCl (0.5molar), the proportion of 8b was significantly lower whereas the yield of 3b (15%) was nearlyunchanged.8b. Yellow oil, 0.88 g, yield 10%; 1H NMR (400 MHz, CDCl3): δH 0.99 (s, 6H, CH2C(Me)2),1.73 (s, 3H, CH=C(Me)2), 1.98 (s, 3H, CH=C(Me)2), 2.13 (s, 3H, NMe), 2.36 (s, 2H,CH2C(Me)2), 5.90 (s, 1H, CH=C(Me)2). 13C NMR (100 MHz, CDCl3): δC 20.35 (q,CH=C(Me)2), 26.54 (q, CH2C(Me)2), 27.41 (q, CH=C(Me)2), 28.46 (q, NMe), 51.42 (t,CH2C(Me)2), 52.71 (s, CH2C(Me)2), 124.89 (d, CH=C(Me)2), 154.91 (s, CH=C(Me)2), 200.45(s, CO). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In water at 20℃; for 48h; | 6-Ethylamino-2,6-dimethylhept-2-en-4-one (8c) To a mixture of 2c (3.31 mL, 2.25 g, 50mmol) and water (5 mL) was added 5 (7.8 mL, 6.90 g, 50 mmol). After stirring at roomtemperature for 48 h, the reaction mixture was acidified with aqueous H2SO4 (15%) and washedwith Et2O (3×). The aqueous solution was made alkaline with aqueous potassium hydroxide (6molar) and extracted with Et2O (3×). The combined organic layers were dried with MgSO4 togive the product 8c after removal of the solvent at reduced pressure.8c. Yellow oil, 7.32 g, yield 80%; IR (νmax, cm-1): 3330 (NH), 2967 (CH), 1675 (CO). 1H NMR(400 MHz, CDCl3): δH 1.08 (t, 3J = 7 Hz, 3H, NCH2CH3), 1.13 (s, 6H, CH2C(Me)2), 1.86 (s, 3H,CH=C(Me)2), 2.11 (s, 3H, CH=C(Me)2), 2.51 (s, 2H, CH2C(Me)2), 2.55 (q, 3J = 7 Hz, 2H,NCH2) 6.03 (s, 1H, CH=C(Me)2). 13C NMR (100 MHz, CDCl3): δC 15.73 (q, NCH2CH3), 20.64(q, CH=C(Me)2), 27.48 (q, CH2C(Me)2), 27.69 (q, CH=C(Me)2), 36.42 (t, NCH2), 52.15 (t,CH2C(Me)2), 53.08 (s, CH2C(Me)2), 125.22 (d, CH=C(Me)2), 155.13 (s, CH=C(Me)2), 200.87(s, CO). HRMS: C11H21NO requires m/z 184.1696. Found 184.1688. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 20℃; for 48h; Overall yield = 36 %; Overall yield = 3.50 g; | 6-Allylamino-2,6-dimethylhept-2-en-4-one (8d) and 2,6-Bis-allylamino-2,6-dimethylheptan-4-one (9d) A mixture of 2d (3.74 mL, 2.85 g, 50 mmol) and water (5 mL) was treatedwith 5 (7.8 mL, 6.90 g, 50 mmol) as described for the reaction of 2c with 5. In this case, amixture (5.77 g) of the products 8d and 9d was obtained. 1H NMR spectra indicated that 8d and9d were formed in an approximate 2:1 ratio.8d. Yellow oil, 3.50 g, yield 36%; 1H NMR (400 MHz, CDCl3): δH 1.12 (s, 6H, CH2C(Me)2),1.84 (br. s, 3H, CH=C(Me)2), 2.12 (s, 3H, CH=C(Me)2), 2.50 (s, 2H, CH2C(Me)2), 3.13 (dt, 3J =5 Hz, 4J = 1.7 Hz, 2H, CH2CH=CH2), 5.02 (dq, 3J =10 Hz, 4J = 1.7 Hz, 1H, CH=CH2), 5.14 (dq,3Jtrans = 17 Hz, 4J = 1.7 Hz, 2H, CH=CH2), 5.87 (ddt, 3Jtrans = 17 Hz, 3Jcis = 10 Hz, 3J = 5 Hz, 1H,CH2CH=CH2), 6.00 (br. s, 1H, -CH=C(Me)2). 13C NMR (100 MHz, CDCl3): δC 20.43 (q,CH=C(Me)2), 27.12 (q, CH2C(Me)2), 45.23 (t, CH2CH=CH2), 52.94 (s, CH2C(Me)2), 53.10 (t,CH2C(Me)2), 115.40 (t, CH=CH2); 126.07 (d, CH=C(Me)2), 137.23 (d, CH2CH=CH2), 155.07(s, CH=C(Me)2), 200.57 (s, C=O). HRMS: C12H21NO requires m/z 196.1690. Found 196.1696.9d. Yellow oil, 2.27 g, yield 36%; 1H NMR (400 MHz, CDCl3): δH 1.11 (s, 12H, CH2C(Me)2),2.50 (s, 4H, CH2C(Me)2), 3.10 (dt, 3J = 5 Hz, 4J = 1.7 Hz, 4H, CH2CH=CH2), 5.02 (dq, 3J =10Hz, 4J = 1.7 Hz, 2H, CH=CH2), 5.14 (dq, 3Jtrans = 17 Hz, 4J = 1.7 Hz, 4H, CH=CH2), 5.87 (ddt,3Jtrans = 17 Hz, 3Jcis = 10 Hz, 3J = 5 Hz, 2H, CH2CH=CH2). 13C NMR (100 MHz, CDCl3): 27.65(q, CH2C(Me)2), 52.51 (s, CH2C(Me)2), 52.53 (t, CH2C(Me)2), 115.40 (t, CH=CH2); 137.13 (d,CH2CH=CH2), 210.86 (s, C=O). picrate of 9d Anal. Calcd for C15H28N2OC6H3N3O7 (487.26):C, 45.64; H, 4.82; N, 15.77%. Found C, 45.33; H, 4.78; N, 12.72%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 20℃; for 48h; Overall yield = 29 %; Overall yield = 3.53 g; | 6-Benzylamino-2,6-dimethylhept-2-en-4-one (8e) and 2,6-Bis-benzylamino-2,6-dimethylheptan-4-one (9e) A mixture of 2e (5.46 mL, 5.36 g, 50 mmol) and water (5 mL) was treatedwith 5 (7.8 mL, 6.90 g, 50 mmol) as described for the reaction of 2c with 5. In this case, amixture (8.63 g) of the products 8e and 9e was obtained. 1H NMR spectra indicated that 8e and9e were formed in an approximate 1:1 ratio.8e. Yellow oil, 3.53 g, yield 29%; 1H NMR (400 MHz, CDCl3): δH 1.18 (s, 6H, CH2C(Me)2),1.84 (s, 3H, CH=C(Me)2), 2.03 (br. s, 1H, NH), 2.09 (s, 3H, CH=C(Me)2), 2.58 (s, 2H,CH2C(Me)2), 3.63 (s, 2H, CH2Ph), 6.01 (br. s, 1H, CH=C(Me)2), 7.17-7.49 (m, 5H, ArH). 13CNMR (100 MHz, CDCl3): δC 20.57 (q, CH=C(Me)2), 27.57 (q, CH2-C(Me)2), 27.62 (q,CH=C(Me)2), 46.32 (t, CH2Ph), 52.30 (t, CH2C(Me)2), 52.97 (s, CH2C(Me)2), 125.17 (d,CH=C(Me)2), 140.68 (s, ArC), 155.00 (s, CH=C(Me)2), 200.58 (s, CO). HRMS: C16H23NOrequires m/z 246.1852. Found 246.1852.9e. Yellow oil, 5.10 g, yield 58%; 1H NMR (400 MHz, CDCl3): δH 1.19 (s, 12H, CH2C(Me)2),2.57 (s, 4H, CH2C(Me)2), 3.67 (s, 4H, CH2Ph), 7.16-7.33 (m, 10H, ArH). 13C NMR (100 MHz,CDCl3): δC 27.45 (q, CH2C(Me)2), 46.81 (t, CH2Ph), 52.30 (t, CH2C(Me)2), 52.89 (s,CH2C(Me)2), 140.68 (s, ArC), 210.91 (s, CO). HRMS: C23H32N2O requires m/z 353.2574. Found353.2587. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 20℃; for 48h; Overall yield = 31 %; Overall yield = 3.22 g; | 6-Butylamino-2,6-dimethylhept-2-en-4-one (8f) and 2,6-Bis-butylamino-2,6-dimethylheptan-4-one (9f) A mixture of 2f (4.94 mL, 3.66 g, 50 mmol) and water (5 mL) was treatedwith 5 (7.8 mL, 6.90 g, 50 mmol) as described for the reaction of 2c with 5. In this case, amixture (6.10 g) of the products 8f and 9f was obtained. 1H NMR spectra indicated that 8f and 9fwere formed in an approximate 3:2 ratio.8f. Yellow oil, 3.22 g, yield 31%; 1H NMR (400 MHz, CDCl3): δH 0.87 (t, 3H, N(CH2)3CH3, 3J= 7 Hz), 1.10 (s, 6H, CH2C(Me)2), 1.32 (m, 2H, N(CH2)2CH2CH3), 1.40 (m, 2H, NCH2CH2),1.68 (br. s, 1H, NH), 1.84 (s, 3H, CH=C(Me)2), 2.09 (s, 3H, CH=C(Me)2), 2.44 (m, 2H, NCH2),2.48 (s, 2H, CH2C(Me)2), 6.02 (br. s, 1H, CH=C(Me)2). 13C NMR (100 MHz, CDCl3): δC 13.99(q, N(CH2)3CH3), 20.59 (t, N(CH2)2CH2CH3), 27.27 (q, CH=C(Me)2), 27.54 (q, CH2C(Me)2),32.90 (t, NCH2CH2), 41.94 (t, NCH2), 52.32 (s, CH2C(Me)2), 52.40 (t, CH2C(Me)2), 125.29 (d,CH=C(Me)2), 154.75 (s, CH=C(Me)2), 200.85 (s, CO). HRMS: C13H25NO requires m/z212.2007. Found 212.2009.9f. Yellow oil, 2.88 g, yield 41%; 1H NMR (400 MHz, CDCl3): δH 0.87 (t, 6H, N(CH2)3CH3, 3J= 7 Hz), 1.09 (s, 12H, CH2C(Me)2), 1.32 (m, 4H, N(CH2)2CH2CH3), 1.40 (m, 4H, NCH2CH2),2.44 (m, 4H, NCH2), 2.48 (s, 4H, CH2C(Me)2). 13C NMR (100 MHz, CDCl3): δC 13.99 (q,N(CH2)3CH3), 20.62 (t, N(CH2)2CH2CH3), 27.62 (q, CH2C(Me)2), 32.92 (t, NCH2CH2), 42.02(t, NCH2), 52.84 (s, CH2C(Me)2), 52.85 (t, CH2C(Me)2), 211.19 (s, CO). HRMS: C17H36N2Orequires m/z 285.2908. Found 285.2900. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ammonium hydroxide at 20℃; for 48h; Overall yield = 19 %; Overall yield = 1.51 g; | 6-Amino-2,6-dimethylhept-2-en-4-one (8a) To an aqueous solution of ammonia (2a) (19%, 22mL) was added phorone (5) (7.8 mL, 6.90 g, 50 mmol). The mixture was stirred at roomtemperature for 48 h until a clear yellow solution had been formed, which was acidified withaqueous hydrogen chloride (0.5 molar) and washed with Et2O (3×). The aqueous solution wasalkalized with the help of aqueous potassium hydroxide (6 molar) and extracted with Et2O (3×).The combined organic layers were dried with MgSO4. After removal of the solvent at reducedpressure, a solid (1.51 g, 19%) remained. 1H NMR spectra indicated that 3a and 8a were formedin an approximate 13:1 ratio.8a. 1H NMR (400 MHz, CDCl3): δH 1.22 (s, 6H, CH2C(Me)2), 1.86 (s, 3H, CH=C(Me)2), 2.12(s, 3H, CH=C(Me)2), 2.52 (s, 2H, CH2C(Me)2), 6.02 (br. s, 1H, CH=C(Me)2). 13C NMR (100MHz, CDCl3): δC 20.58 (q, CH=C(Me)2), 27.61 (q, CH2C(Me)2), 30.47 (q, CH=C(Me)2), 49.06(s, CH2C(Me)2), 56.06 (t, CH2C(Me)2), 124.87 (d, CH=C(Me)2), 155.44 (s, CH=C(Me)2),200.43 (s, C=O). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With MgO/ZrO2 mixed oxides at 449.84℃; | Acetone self-condensation General procedure: A 150 mg sample of each catalyst was placed in a 0.4 cm i.d. Ushapedquartz tube located in a PID- controlled furnace. This reactorwas connected to the reaction initial gas flow. The acetone wasinjected by a syringe pump as a liquid in a He flow (0.05 L/min) andvaporized in situ, obtaining a volume concentration of 3.2%. Outgoinggases from the reactor were analyzed online by a ShimadzuGC-2010 gas chromatograph with a FID detector. Before any batch,the catalyst was pretreated in He at 723 K for 1 h. The acetone gas phase condensation was studied in a temperature range from 473to 723 K with steps of 50 K. More details about the reaction proce-dure, the reactor configuration and equipment were described inprevious studies [3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With MgO/ZrO2 mixed oxides at 449.84℃; | Acetone self-condensation General procedure: A 150 mg sample of each catalyst was placed in a 0.4 cm i.d. Ushapedquartz tube located in a PID- controlled furnace. This reactorwas connected to the reaction initial gas flow. The acetone wasinjected by a syringe pump as a liquid in a He flow (0.05 L/min) andvaporized in situ, obtaining a volume concentration of 3.2%. Outgoinggases from the reactor were analyzed online by a ShimadzuGC-2010 gas chromatograph with a FID detector. Before any batch,the catalyst was pretreated in He at 723 K for 1 h. The acetone gas phase condensation was studied in a temperature range from 473to 723 K with steps of 50 K. More details about the reaction proce-dure, the reactor configuration and equipment were described inprevious studies [3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | With cesium fluoride In dimethyl sulfoxide at 100℃; for 24h; Autoclave; Schlenk technique; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With bis(pinacolato)diborane In tert-butyl methyl ether at 70℃; for 24h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | at 120℃; for 22h; Inert atmosphere; Schlenk technique; | 1.c c) Preparation of 1,2-bis(4-phosphonone)o-xylene: Under an inert gas atmosphere, in a 50 mL Schlenk flask, add 340 mg of 1,2-diphosphine hydrogen-o-xylene and 0.65 mL of 2,6-dimethyl-2,5-heptadien-4-one (alkenyl ligand) was heated to 120° C. and reacted for 22 hours. After the reaction, return to room temperature, add a small amount of methanol to the yellow oil for recrystallization, stand at low temperature overnight and filter to obtain 1,2-bis(4-phosphonone)o-xylene with a yield of 91%. |
47% | at 120℃; for 22h; | 2 Synthesis of 1,2-Bis[(2,2,6,6-tetramethylphosphinan-4-onyl)methyl]benzene (BPX) 1,2-Bis(phosphinomethyl)benzene (3.40 g, 20.0 mmol) and 2,6-dimethylhepta-2,5-dien-4-one (6.25 mL, 40.0 mmol) were heated to 120°C for 22 hours. Upon cooling, a very viscous yellow oil was formed which crystallised on standing. The yellow crystals were triturated in MeOH overnight, filtered and recrystallised in boiling MeOH to yield BPX as a white solid (4.2 g, 47%). 1H NMR (400 MHz, CDCl3): δ 7.50 - 7.40 (2H, m, ArH), 7.15 - 7.12 (2Η, m, ArH), 3.25 (4Η, s, PCH2), 2.56 - 2.52 (4Η, m, CH2), 2.39 - 2.31 (4Η, m, CH2), 1.20 ( 12Η, d, 3JPH = 5.4 Hz, CH3) and 1.07 ppm ( 12H, d, 3JPH = 17.0 Hz, CH3). 13C NMR (101 MHz, CDCl3): δ 209.9 (d, 3JCP = 1.1 Hz, C=0), 136.9 (dd, 2JCP = 7.7 Hz, 3JCP = 2.9 Hz, ArCq), 131.3 (d, 3JCP = 11.2 Hz, ArC), 126.4 (d, 4JCP = 1.8 Hz, ArC), 55.5 (d, 1JCP = 6.4 Hz, CH2), 35.4 (d, 1Jcp 19.1 Hz Cq), 31.7 (d, 2JCP = 25.2 Hz, CH3), 26.4 (dd, 1Jcp 26.7 Hz and 4JCP = 8.7 Hz, PCH2) and 25.8 (s, CH3). 31P NMR ( 162 MHz, CDCl3): δ 5.6 ppm. IR (KBr): v 1700 (s) C=0 str. Elem. Anal. Calcd for C26H40O2P2: C, 69.93; H, 9.03. Found: C, 70.14; H, 8.82. |
4.2 g | In neat (no solvent) at 120℃; for 22h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | at 120℃; for 36h; | 2 Synthesis of 1,3-bis(4-phosphorinone)propane, BPPr. 1,3-Bis(phosphino)propane (3.6 g,18.5wt%, 6.2 mmol) and phorone (1.8 g, 13.0 mmol) were heated at 120 °C for 36 hours. The resulting sticky solid was washed with pentane (10 mL) and dried in vacuo to furnish a white solid (0.94 g, 40% yield). 1H NMR (400 MHz, CDCl3): δ 2.41 - 2.35 (8H, m, CH2CO), 1.90 - 1.78 (2Η, m, CH2), 1.71 - 1.67 (4Η, m, PCH2), 1.20 (12Η, d, 3JpH = 16.2 Hz, CH3) and 1.13 ppm (12H, d, 3JPH = 8.0 Hz, CH3). 13C{1H} NMR (101 MHz, CDCl3): δ 210.7 (C=O), 53.9 ( H2CO), 34.7 (d, 1JCP = 17.5 Hz, Cq), 31.2 (d, 2JCP = 25.7 Hz, CH3), 28.6 (t, 2JCp = 9.3 Hz, CH2), 27.4 (d, 2JCP = 4.8 Hz, CH3) and 22.8 ppm (dd, 3JCp = 22.7 Hz and 3JCP = 13.4 Hz, P CH2). 31P{1H} NMR (162 MHz, CDCl3): δ 6.4 ppm. HR-MS (+ve ESI): 385.2432 [M + H]+ calc. 385.2420. Elem. Anal. Calcd for C21H38O2P2: C, 65.60; H, 9.96. Found: C, 65.50; H, 9.85. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | at 120℃; for 20h; Inert atmosphere; | 31 Preparation of -(P-(2,2,6,6,-tetramethylphosphinan-4-one))dimethylferroce□,□1,2-bis-ne 2,6-Dimethyl-2,5-heptadiene-4-one (14.6 g, 0.106 mol) is added to 170 1,2-bis-(diphosphinomethyl)ferrocene (Example 30, 14.7 g, 0.053 mol) and the mixture heated to 120° C. under nitrogen for 20 hours. The reaction mixture is cooled, the crude title compound removed by filtration, washed with pentene (20 ml) and dried in vacuo to yield the 174 title compound as a yellow-orange solid (24.9 g, 85% yield). The title compound was characterised by 31P NMR and mass spectrum. 1H NMR (250 MHz; CDCl3): d 4.32 (1H, br); 4.08 (5H, br); 4.02 (1H, br); 3.94 (1H br); 2.84 (4H, br); 1.8-2.5 (8H, br); 1.05-1.4 (24H, br). 31P NMR (101 MHz; CDCl3): s 4.15 ppm. Elemental analysis: Found: C, 64.26%; H, 7.88%. Calculated: C, 65.03%; H, 7.94%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With 1,1,1,3',3',3'-hexafluoro-propanol at 50℃; | |
66% | at 160℃; for 22h; Inert atmosphere; | |
Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With C20H29ClO2P2Pt In water; toluene at 105℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride at 105℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 1,1,1,3',3',3'-hexafluoro-propanol / 50 °C 2: toluene-4-sulfonic acid / toluene / 115 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: Heating 2: toluene / 115 °C 3: boron trifluoride diethyl etherate / dichloromethane / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: Heating 2: toluene / 115 °C 3: boron trifluoride diethyl etherate / dichloromethane / -78 °C 4: potassium hydroxide; hydrazine / diethylene glycol / 210 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: Heating 2: toluene / 115 °C 3: potassium hydroxide; hydrazine / diethylene glycol / 180 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: Heating 2: toluene / 115 °C 3: boron trifluoride diethyl etherate / dichloromethane / -78 °C 4: boron trifluoride diethyl etherate / dichloromethane / -78 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: Heating 2: toluene / 115 °C 3: boron trifluoride diethyl etherate / dichloromethane / -78 °C 4: boron trifluoride diethyl etherate / dichloromethane / -78 °C 5: potassium hydroxide; hydrazine / diethylene glycol / 210 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium isopropylate In isopropyl alcohol at 20 - 60℃; for 6h; | 1.2; 2.2; 3.2; 4.2; 1.2; 2.2 Step 2 Add 1-nitroso 2,2,6,6-tetramethyl-piperidone (600g, 3.26mol) into a 10L three-necked flask,4.5L isopropanol, sodium isopropoxide (35g, 0.43mol),Control the temperature at 2060, stop the reaction after 6 hours,Distill out isopropanol under reduced pressure, add 600ml water to the concentrate,Extract with 1.2L of n-hexane, dry with anhydrous magnesium sulfate,Filter, distill off n-hexane under reduced pressure, freeze, filter,405 g of light yellow crystals were obtained (yield 90%, GC=99.71%). |
Tags: 504-20-1 synthesis path| 504-20-1 SDS| 504-20-1 COA| 504-20-1 purity| 504-20-1 application| 504-20-1 NMR| 504-20-1 COA| 504-20-1 structure
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