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CAS No. : | 56-37-1 | MDL No. : | MFCD00011824 |
Formula : | C13H22ClN | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | HTZCNXWZYVXIMZ-UHFFFAOYSA-M |
M.W : | 227.77 | Pubchem ID : | 66133 |
Synonyms : |
|
Num. heavy atoms : | 15 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.54 |
Num. rotatable bonds : | 5 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 68.48 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -8.45 cm/s |
Log Po/w (iLOGP) : | -1.5 |
Log Po/w (XLOGP3) : | -1.07 |
Log Po/w (WLOGP) : | -0.08 |
Log Po/w (MLOGP) : | -0.08 |
Log Po/w (SILICOS-IT) : | 2.87 |
Consensus Log Po/w : | 0.02 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.54 |
Solubility : | 65.1 mg/ml ; 0.286 mol/l |
Class : | Very soluble |
Log S (Ali) : | 1.56 |
Solubility : | 8250.0 mg/ml ; 36.2 mol/l |
Class : | Highly soluble |
Log S (SILICOS-IT) : | -5.24 |
Solubility : | 0.00132 mg/ml ; 0.00000581 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.04 |
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 |
---|---|---|
at 120℃; for 0.08333330000000001h;Green chemistry; | 5.19 g (41 mmol) of benzyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.15 g (41 mmol) of triethylamine (manufactured by Wako Pure Chemical Industries Ltd.) were stirred and mixed at room temperature,And heated at 120 C. for 5 minutes. The resulting white solid was dissolved in methanol, filtered, and concentrated to obtain the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With trimethylsilyl iodide In acetonitrile for 0.5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.4% | With sodium hydroxide; In chloroform; water; at 20℃; | In chloroform (12 mL) was dissolved 305 mg (1.86 mmol) of 1-(methoxymethoxy)-2-vinylbenzene obtained in Example 7(2), 5 mL (63 mmol) of 50% aqueous sodium hydroxide solution was added dropwise to the solution, and then, 54.1 mg (0.237 mmol) of benzyl(triethyl)ammonium chloride was added to the same and the resulting mixture was stirred at room temperature overnight. The reaction mixture was poured into water, and extracted with chloroform. The organic layer was successively washed with water and brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off and the obtained residue was purified by preparative thin-layer chromatography (available from MERCK CO., 1.05744, 3 plates were used, developed by ethyl acetate:hexane=1:2) to obtain 387 mg (1.57 mmol, Yield: 84.4%) of 1-(2,2-dichlorocyclopropyl)-2-(methoxymethoxy)benzene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium azide; In acetonitrile; | A mixture of benzyl triethylammonium chloride (2.0 kg) and sodium azide (0.69 kg) was slurried together in MeCN (12 kg). The insoluble sodium chloride was removed by filtration and the filtrate washed with MeCN. To a homogenous mixture of Vc (1.9 kg), 4-NMM (0.26 kg) and THF (7.6 L) was added the MeCN solution of benzyl triethylammonium azide which produced a clear solution. A solution of iodine (2.45 kg) in THF (10 L) was added slowly while maintaining the internal temperature at 0-5 C. After the addition was completed the reaction mixture was aged at 5-10 C for ca. 2 h. Excess azide was destroyed by adding small amounts of N-acetyl cysteine (40 g) before proceeding. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79.3% | With Iodine monochloride; In dichloromethane; water; for 0.75h; | To a stirred solution of ICI (146.1 g, 900 mmol) in 2 L of DCM was added BnEtsNCb (146.1 g, 900 mmol) in 1 L of water via an addition funnel over 15 min. After stirring for 30 min the layers were separated, and the organic layer was dried (magnesium sulfate), filtered, and concentrated under reduced pressure. The residue was crystallized by taking it up in minimal DCM and back adding ether to a 3: 1 (DCM: ether) ratio. The material was filtered and washed with ether to yield 278 g (79.3% yield) of yellow crystals. |
79.3% | With Iodine monochloride; In dichloromethane; water; for 0.75h; | To a stirred solution of ICI (146.1 g, 900 mmol) in 2 L of DCM was added BnEt3NCl2 (146.1 g, 900 mmol) in 1 L of water via an addition funnel over 15 min. After stirring for 30 min the layers were separated, and the organic layer was dried (magnisium sulfate), filtered, and concentrated under reduced pressure. The residue was crystallized by taking it up in minimal DCM and back adding ether to a 3: 1 (DCM: ether) ratio. The material was filtered and washed with ether to yield 278 g (79.3% yield) of yellow crystals. |
58% | With Iodine monochloride; In dichloromethane; for 1.0h; | 11 Commercially available benzyltriethylammonium chloride (10,2. 00 g, 8.79 MMOL) was added to a clean 25 mL vial. This vial was capped and shaken until all of the solid dissolved. To a separate clean 25 mL vial was added iodine MONOCHLORIDE (834 mg, 5.126 MMOL) and distilled CH2CI2 (10 mL). The aqueous solution from the first vial was transferred to the second vial with a pipette. The resulting biphasic solution was tightly capped and shaken with a mechanical shaker for 1 h. The organic phase was extracted, dried over MGSO4, filtered, and concentrated to dryness. No further purification was necessary. This reaction provided 1.98 g (58 %) of 11 as an orange SOLID. H NMR (300 MHZ, CDCI3) : 6 7.48 (m, 5H), 4.43 (s, 2H), 3.29 (m, 6H), 1.50 (m, 9H) ; 13C NMR (75.5 MHZ, CDCI3) : 6 132.9, 131.3, 129.9, 126.0, 61.3, 53.1, 8.4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
17% | With sodium bicarbonate;palladium diacetate; In water; N,N-dimethyl-formamide; | (202-2) Under nitrogen atmosphere, a suspension of <strong>[289039-82-3]methyl 5-chloro-2-iodobenzoate</strong> (Example 109-9) (220 mg), the compound of Example 202-1 (200 mg), Pd(OAc)2 (22.9 mg), BnEt3NCl (171 mg), sodium hydrogen carbonate (130 mg), tri-o-tolylphosphine (68.4 mg) in DMF (4.0 mL) was stirred at 80 C. for 4 hours, and stirred at 100 C. for 11 hours, during which silver (I) carbonate (207 mg) was added thereto. The mixture was cooled to room temperature, and the mixture was filtered. Water was added to the filtrate, and the mixture was extracted with ethyl acetate/toluene. The organic layer was washed with water and a saturated brine, and dried over MgSO4. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column (hexane/ethyl acetate=7/1?5/1) to give methyl 5-chloro-2-{(1E)-4-[2-(4-methoxybenzoyl)-4-methyl-1H-pyrrol-1-yl]-1-butenyl}benzoate (55.0 mg, 17%). 1H NMR (CDCl3, 400 MHz) delta 7.81 (d, 1H, J=2.2 Hz), 7.77 (d, 2H, J=8.8 Hz), 7.36 (d, 1H, J=8.5 Hz), 7.32 (dd, 1H, J=2.2, 8.5 Hz), 7.10 (d, 1H, J=15.7 Hz), 6.90 (d, 2H, J=8.8 Hz), 6.77 (d, 1H, J=1.4 Hz), 6.51 (d, 1H, J=1.4 Hz), 6.08 (dt, 1H, J=15.7, 7.1 Hz), 4.49 (t, 2H, J=7.1 Hz), 3.89 (s, 3H), 3.87 (s, 3H), 2.72 (dt, 2H, J=7.1, 7.1 Hz), 2.07 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In tetrahydrofuran; water; | Compound (3) Compound (3) can be prepared according to the following procedure. Carbazole (16.7 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), 1-bromopentane (15.1 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), and benzyltriethyl ammonium chloride (1.7 g) are dissolved in tetrahydrofuran (60 mL) and a concentrated solution of sodium hydroxide (17 g) in water (17 mL) is added. The mixture is heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated is filtered off and the tetrahydrofuran layer is dried (MgSO4) and concentrated to dryness. The combined organic solids were recrystallized to form 9-pentylcarbazole. | |
With sodium hydroxide; In water; toluene; | Preparation of N-Pentyl-3-formyl Carbazole This material was prepared according to the following procedure Step one:-Preparation of N-Pentylcarbazole:-To a 1 liter 3-neck round bottom flask equipped with reflux condenser and mechanical stirrer were added 250 g carbazole (1.5 mol; obtained from Aldrich Chemicals; Milwaukee; Wis.), 241.7 g 1-bromopentane (1.6 mol; obtained from Aldrich Chemicals; Milwaukee; Wis.), 17 g benzyltriethyl ammonium chloride (0.075 mol; obtained from Aldrich Chemicals; Milwaukee; Wis.) and 1000 ml of toluene. The mixture was stirred at room temperature for 0.5 hr., followed by the addition of an aqueous solution of NaOH (prepared by dissolving 300 g of NaOH in 300 g water). The mixture was refluxed for 5 hours and cooled to room temperature. The organic phase was separated and washed repeatedly with water until the pH of the washing water was neutral. | |
With sodium hydroxide; In tetrahydrofuran; water; | Compound (15) Compound (15) can be prepared according to the following procedure. Carbazole (16.7 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), 1-bromopentane (15.1 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), and benzyltriethyl ammonium chloride (1.7 g) are dissolved in tetrahydrofuran (60 mL) and a concentrated solution of sodium hydroxide (17 g) in water (17 mL) is added. The mixture is heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated is filtered off and the tetrahydrofuran layer is dried (MgSO4) and concentrated to dryness. The combined organic solids were recrystallized to form 9-pentylcarbazole. |
With sodium hydroxide; In tetrahydrofuran; water; | Compound (19) Compound (19) can be prepared according to the following procedure. Carbazole (16.7 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), 1-bromopentane (15.1 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), and benzyltriethyl ammonium chloride (1.7 g) are dissolved in tetrahydrofuran (60 mL) and a concentrated solution of sodium hydroxide (17 g) in water (17 mL) is added. The mixture is heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated is filtered off and the tetrahydrofuran layer is dried (MgSO4) and concentrated to dryness. The combined organic solids were recrystallized to form 9-pentylcarbazole. | |
With sodium hydroxide; In tetrahydrofuran; water; | Compound (23) Compound (23) can be prepared according to the following procedure. Carbazole (16.7 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), 1-bromopentane (15.1 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), and benzyltriethyl ammonium chloride (1.7 g) are dissolved in tetrahydrofuran (60 mL) and a concentrated solution of sodium hydroxide (17 g) in water (17 mL) is added. The mixture is heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated is filtered off and the tetrahydrofuran layer is dried (MgSO4) and concentrated to dryness. The combined organic solids were recrystallized to form 9-pentylcarbazole. | |
With sodium hydroxide; In tetrahydrofuran; water; | Compound (29) Compound (29) can be prepared according to the following procedure. Carbazole (16.7 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), 1-bromopentane (15.1 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), and benzyltriethyl ammonium chloride (1.7 g) are dissolved in tetrahydrofuran (60 mL) and a concentrated solution of sodium hydroxide (17 g) in water (17 mL) is added. The mixture is heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated is filtered off and the tetrahydrofuran layer is dried (MgSO4) and concentrated to dryness. The combined organic solids were recrystallized to form 9-pentylcarbazole. | |
With sodium hydroxide; In tetrahydrofuran; water; | Compound (33) Compound (33) can be prepared according to the following procedure. Carbazole (16.7 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), 1-bromopentane (15.1 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), and benzyltriethyl ammonium chloride (1.7 g) are dissolved in tetrahydrofuran (60 mL) and a concentrated solution of sodium hydroxide (17 g) in water (17 mL) is added. The mixture is heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated is filtered off and the tetrahydrofuran layer is dried (MgSO4) and concentrated to dryness. The combined organic solids were recrystallized to form 9-pentylcarbazole. | |
With sodium hydroxide; In tetrahydrofuran; water; | Compound (37) Compound (37) can be prepared according to the following procedure. Carbazole (16.7 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), 1-bromopentane (15.1 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), and benzyltriethyl ammonium chloride (1.7 g) are dissolved in tetrahydrofuran (60 mL) and a concentrated solution of sodium hydroxide (17 g) in water (17 mL) is added. The mixture is heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated is filtered off and the tetrahydrofuran layer is dried (MgSO4) and concentrated to dryness. The combined organic solids were recrystallized to form 9-pentylcarbazole. | |
With sodium hydroxide; In tetrahydrofuran; water; | Compound (41) Compound (41) can be prepared according to the following procedure. Carbazole (16.7 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), 1-bromopentane (15.1 g, 0.1 mol, commercially available from Aldrich, Milwaukee, Wis.), and benzyltriethyl ammonium chloride (1.7 g) are dissolved in tetrahydrofuran (60 mL) and a concentrated solution of sodium hydroxide (17 g) in water (17 mL) is added. The mixture is heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated is filtered off and the tetrahydrofuran layer is dried (MgSO4) and concentrated to dryness. The combined organic solids were recrystallized to form 9-pentylcarbazole. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40.4 g (86.5%) | In tetrahydrofuran; sodium hydroxide; | a) A solution of 4-chloro-3-(trifluoromethyl)benzeneacetonitrile (0.114 mol) in THF (100 ml) was added dropwise at RT to a solution of <strong>[20098-48-0]1,2,3-trichloro-5-nitrobenzene</strong> (0.114 mol) and N,N,N-triethylbenzenemethanaminium chloride (3 g) in NaOH (150 ml) and THF (100 ml). The mixture was stirred at RT for 2 hours, then poured out on ice, acidified with a concentrated HCl solution and extracted with CH2Cl2. The organic layer was separated, dried, filtered and the solvent was evaporated. The residue was crystallized from DIPE. The precipitate was filtered off and dried, yielding 40.4 g (86.5%) of (+-)-2,6-dichloro-alpha-[4-chloro-3-(trifluoromethyl)phenyl]-4-nitrobenzene-acetonitrile (interm. 1). |
40.4 g (86.5%) | In tetrahydrofuran; sodium hydroxide; | a) A solution of 4-chloro-3-(trifluoromethyl)benzeneacetonitrile (0.114 mol) in THF (100 ml) was added dropwise at RT to a solution of <strong>[20098-48-0]1,2,3-trichloro-5-nitrobenzene</strong> (0.114 mol) and N,N,N-triethylbenzenemethanaminium chloride (3 g) in NaOH (150 ml) and THF (100 ml). The mixture was stirred for 2 hours, then poured out on ice, acidified with a concentrated HCl solution and extracted with CH2Cl2. The organic layer was separated, dried, filtered and the solvent was evaporated. The residue was crystallized from DIPE. The precipitate was filtered off and dried, yielding 40.4 g (86.5%) of (+-)-2,6-dichloro-alpha-[4-chloro-3-(trifluoromethyl)phenyl]-4-nitrobenzene-acetonitrile (interm. 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water; toluene | 10 Preparation of 16α,17β-Dihydroxy-estra-1,3,5(10)-trien-3-yl N,N-diethyl-sulfamate Preparation of 16α,17β-Dihydroxy-estra-1,3,5(10)-trien-3-yl N,N-diethyl-sulfamate 2 g of estriol, 5.2 g of sodium hydroxide, 1.72 g of triethyl benzyl ammonium chloride and 9.75 ml of N,N-diethyl-amidosulfonyl chloride are reacted as described in Example 1 in a mixture of 800 ml of toluene and 128 ml of water. The title compound is obtained after reprocessing, chromatographic purification, and recrystallizing from acetone. Fp.: 121-124° C.; [α]D: +44° C. (chloroform, c=1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water; toluene | 6 Preparation of 16α,17β-Dihydroxy-estra-1,3,5(10)-trien-3-yl N,N-dimethyl-sulfamate Preparation of 16α,17β-Dihydroxy-estra-1,3,5(10)-trien-3-yl N,N-dimethyl-sulfamate 120 ml of water, 1.58 g of benzyl triethyl ammonium chloride, 7.44 ml of N,N-dimethyl-amidosulfonyl chloride and 4 ml of 40% aqueous sodium hydroxide solution are mixed under stirring with a solution of 2 g estriol in 800 ml of toluene at a temperature of 80° C. The batch is heated to 80° C. The reaction solution is kept at a pH value of 10 during this time by adding 40% aqueous sodium hydroxide solution. The batch is allowed to cool down to room temperature when the parent compounds have been reacted completely, and worked-up as described in Example 1. The residue obtained is recrystallized from acetone/n-hexane and yield the title compound. Fp.: 180-181° C.; [α]D: +48° C. (chloroform, c=1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroborane diethyl ether; In thionyl chloride; | Example 1 2-Chloromethyl-4-cyano-benzoyl chloride 1-Oxo-1,3-dihydro-isobenzofuran-5-carbonitrile (25 g), boron trifluoride etherate (0.8ml), and benzyl triethyl ammonium chloride (0.72 g) were suspended in thionyl chloride (92 ml) and heated to reflux for 17 hours. Excess thionyl chloride was removed by distillation under nitrogen to give an internal temperature of 95° C., and heating to reflux was continued for another 24 hours. The product was purified by distillation under reduced pressure. Yield: 27.5 g, 92percent. Melting point 44 -44.5 C. 1H NMR (CDCl3, 400 MHz): 4.83 (2H, s), 7.74 (1H, dd, J=1, 8 Hz), 7.89 (1H, d, J=1 Hz), 8.25 (1H, d, J=8 Hz). 13C NMR (CDCl3, 100 MHz): 42.7, 116.8, 118.0, 132.2, 133.8, 134.0, 135.7, 140.0, 166.9. IR (KBr): v 3108, 3077, 2963, 2239, 1755, 1604, 1298, 1195, 1103, 944, 935, 840 cm-1. | |
With thionyl chloride; trifluoroborane diethyl ether; In 5,5-dimethyl-1,3-cyclohexadiene; | Example 2 2-Chloromethyl-4-cyano-benzoyl chloride 1-Oxo-1,3-dihydro-isobenzofuran-5-carbonitrile (80 g), boron trifluoride etherate (4,4 ml), benzyltriethyl ammonium chloride (9,2 g), and thionyl chloride (55 ml) were suspended in xylene (320 ml). The mixture was heated to reflux for 4 hours and volatiles were removed under reduced pressure. The product was purified by distillation under high vacuum. Yield: 78,2 g, 73percent. Melting point 44 -44.5° C. 1H NMR (CDCl3, 400 MHz): 4.83 (2H, s), 7.74 1H, dd, J=1, 8 Hz), 7.89 1H, d, J=1 Hz), 8.25 1H, d, J=8 Hz). 13C NMR (CDCl3, 100 MHz): 42.7, 116.8, 118.0, 132.2, 133.8, 134.0, 135.7, 140.0, 166.9. IR (KBr): v 3108, 3077, 2963, 2239, 1755, 1604, 1298, 1195, 1103, 944, 935, 840 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.4 g (56%) | With sodium hydroxide; In tetrahydrofuran; water; | EXAMPLE B.4 Iodomethane (0.38 ml) was added dropwise at room temperature to a solution of compound (8) (2.44 g) and <strong>[56-37-1]N,N,N-triethylbenzenemethanaminium chloride</strong> (0.54 g) in tetrahydrofuran (30 ml) and sodium hydroxide (40%) (30 ml) and the mixture was stirred at room temperature for 3 hours. Water was added and the mixture was extracted with ethyl acetate. The organic layer was dried, filtered off and evaporated. The residue was purified by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 96.5/3.5/0.1). The pure fractions were collected, evaporated and crystallized from 2-propanone and DIPE. The precipitate was filtered off, washed with diethyl ether and dried, yielding 1.4 g (56%) of (+-)-4-(3-chlorophenyl)-6-[(1-butyl-1H-imidazol-5-yl)(4-chlorophenyl)hydroxymethyl]-1-methyl-2(1H)-quinolinone; (comp. 9, mp. 174.6 C). |
1.4 g (56%) | With sodium hydroxide; In tetrahydrofuran; water; | Example B.4 Iodomethane (0.38 ml) was added dropwise at room temperature to a solution of compound (8) (2.44 g) and <strong>[56-37-1]N,N,N-triethylbenzenemethanaminium chloride</strong> (0.54 g) in tetrahydrofuran (30 ml) and sodium hydroxide (40%) (30 ml) and the mixture was stirred at room temperature for 3 hours. Water was added and the mixture was extracted with ethyl acetate. The organic layer was dried (MgSO4), filtered off and evaporated. The residue was purified by column chromatography over silica gel (eluent: CH2 Cl2 /CH3 OH/NH4 OH 96.5/3.5/0.1). The pure fractions were collected, evaporated and crystallized from 2-propanone and DIPE. The precipitate was filtered off, washed with diethyl ether and dried, yielding 1.4 g (56%) of (+-)-4-(3-chlorophenyl)-6-[(1-butyl-1H-imidazol-5-yl)(4-chlorophenyl)hydroxymethyl]-1-methyl-2(1H)-quinolinone; (comp. 9, mp. 174.6 C.). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18,8 g (85%) | With sodium hydroxide; In water; | 1-(4-Bromophenyl)-cyclopropanecarbonitrile (Intermediate 113) To a 50% aqueous NaOH solution (40.0 g, wt/wt) was added benzyl triethylammonium chloride (1.0 g, 4.4 mmols), 4-bromobenzonitrile (19.6 g, 0.10 mol), and 1,2-dibromoethane (56.4 g, 0.30 mol). The mixture was stirred overnight at room temperature and then diluted with 100 mL of H2O. This mixture was extracted with EtOAc and the combined extracts were washed with saturated aqueous NaHS2O3, H2O, and saturated aqueous NaCl before being dried (MgSO4) and concentrated under reduced pressure. Bulb-to-bulb distillation afforded 18,8 g (85%) of the title compound as a colorless solid. 1H NMR (CDCl3) delta: 7.48 (2H, d, J=8.6 Hz), 7.17 (2H, d, J 8.6 Hz), 1.75 (2H, dd, J=5.2, 7.6Hz), 1.39 (2H, dd, J=5.2, 7.6 Hz). |
18.8 g (85%) | With sodium hydroxide; In water; | 1-(4-Bromophenyl)-cyclopropanecarbonitrile (Intermediate 113) To a 50% aqueous NaOH solution (40.0 g, wt/wt) was added benzyl triethylammonium chloride (1.0 g, 4.4 mmols), 4-bromobenzonitrile (19.6 g, 0.10 mol), and 1,2-dibromoethane (56.4 g, 0.30 mol). The mixture was stirred overnight at room temperature and then diluted with 100 mL of H2O. This mixture was extracted with EtOAc and the combined extracts were washed with saturated aqueous NaHS2O3, H2O, and saturated aqueous NaCl before being dried (MgSO4) and concentrated under reduced pressure. Bulb-to-bulb distillation afforded 18.8 g (85%) of the title compound as a colorless solid. 1H NMR (CDCl3) delta: 7.48 (2H, d, J=8.6 Hz), 7.17 (2H, d, J=8.6 Hz), 1.75 (2H, dd, J=5.2, 7.6 Hz), 1.39 (2H, dd, J=5.2, 7.6 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trichlorophosphate; In acetonitrile; | Step A: 4-Chloro-2-hydroxy-3-nitropyridine Phosphorous oxychloride (63.4 mL, 0.68 mol) was added dropwise to a stirred mixture of <strong>[89282-12-2]2,4-dihydroxy-3-nitropyridine</strong> (28.92 g, 0.17 mol) and benzyl triethylammonium chloride (155 g, 0.68 mol) in acetonitrile (560 mL). The reaction mixture was warmed to 60 C. for 1 h then was heated to reflux for 1 h. The reaction was cooled and the volatiles were evaporated in vacuo. An ice/water slurry (500 mL) was added to the residual oil and the mixture was stirred for 3 h at 0 C. The solids were collected by filtration, washing with water and hexanes to give the title compound as a solid; NMR (CD3 OD); d 2.33 (s, 3H), 6.39 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In ethyl acetate n-hexane; dichloromethane; water; | a) 6-(1-Cyanoethyl)-1-{3-{2(E)-(7-chloroquinolin-2-yl)ethenyl}benzyl]indole A solution of 6-(cyanomethyl)-1-[3-{2(E)-(7-chloroquinolin-2-yl)ethenyl}benzyl]indole (Example 29b) (180 mg, 0.41 mmol), methyl iodide (77 mul, 1.24 mmol) and <strong>[56-37-1]benzyl-triethyl-ammonium chloride</strong> (94 mg, 0.41 mmol) in dichloromethane (3 ml) was stirred with a solution of sodium hydroxide (1.5 g) in water (1.5 ml) heating under reflux for 2 hours. The mixture was diluted with dichloromethane and water and the aqueous layer was extracted with further dichloromethane. The combined solvent layer was dried and evaporated and the residue was chromatographed on silica in ethyl acetate-hexane (1:3). The resulting crude product was further purified by RP-HPLC on a C18 column (eluding with 85 methanol:15 water:0.1 acetic acid) followed by crystallisation from methanol-water. | |
With sodium hydroxide; In ethyl acetate n-hexane; dichloromethane; water; | a) 6-(1-Cyanoethyl)-1-{3-{2(E)-(7-chloroquinolin-2-yl)ethenyl}benzyl]indole A solution of 6-(cyanomethyl)-1-[3-{2(E)-(7-choroquinolin-2-yl)ethenyl}benzyl]indole (Example 29b) (180 mg, 0.41 mmol), methyl iodide (77mul, 1.24 mmol) and <strong>[56-37-1]benzyl-triethyl-ammonium chloride</strong> (94 mg, 0.41 mmol) in dichloromethane (3 ml) was stirred with a solution of sodium hydroxide (1.5 g) in water (1.5 ml) heating under reflux for 2 hours. The mixture was diluted with dichloromethane and water and the aqueous layer was extracted with further dichloromethane. The combined solvent layer was dried and evaporated and the residue was chromatographed on silica in ethyl acetate-hexane (1:3). The resulting crude product was further purified by RP-HPLC on a C18 column (eluding with 85 methanol:15 water:0.1 acetic acid) followed by crystallisation from methanol-water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With sodium hydroxide; In dichloromethane; water; | Step 1 Preparation of 2-(diphenylmethylimino)-6-heptenenitrile A 12.0 g sample (54.4 mmol) of 2-(diphenylmethylimino)acetonitrile was dissolved in 70 mL of dichloromethane. A 1.3 g sample (5.3 mmol) of benzyltriethylammoniumchloride and 15 mL 50% NaOH were added to the ice-cooled solution. Over a period of 2 hours, 13.2 g of 5-bromo 1-pentene (88.6 mmol) was slowly added under vigorous stirring. The mixture was stirred for another 22 hours, which was interrupted by addition of two 5-mL portions of 50% NaOH after 4 hours and 20 hours. The dark red mixture was then poured into a separatory funnel containing 100 mL of water and 100 mL of dichloromethane. The aqueous layer was extracted with three 50-mL portions of dichloromethane. The organic layer was then washed with two 50-mL portions of water, and finally with 50 mL of a saturated sodium chloride solution. After removal of the solvent and drying over magnesium sulfate, the crude product was purified by carrying out a Kugelrohr distillation, yielding 10.2 of product (56% yield). [characterization: 1 H-NMR (CDCl3): delta=1.54 (m, 2H); delta=2.01 (m, 4H); delta=4.23 (m, 1H); delta=4.93 (m, 2H); delta=5.72 (m, 1H); delta=7.50 (m, 10H)] |
Yield | Reaction Conditions | Operation in experiment |
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With sodium hydroxide; In chloroform; | To (Z)-1-[4-(2-methoxyethoxy)phenyl]-2-phenylethylene (15.61 g, 0.06 mol) dissolved in CHCl3 (193 mL) was added triethylbenzyl-ammonium chloride (0.98 g, 0.004 mol), chilled 40% NaOH solution (96.00 g, 2.40 mol) was added slowly through a dropping funnel according to the method of Dehmlow and Schonefeld, J. Lebigs Ann Chem., 744:42(1971) and the mixture stirred for 80 hours. The resulting brown emulsion was poured onto 200 mL water in a separatory funnel and the layers were separated, the aqueous layer was extracted with three 50 mL portions of CH2 Cl2, the combined organic extracts were washed with brine, dried over MgSO4, filtered and evaporated in vacuo to obtain a dark brown oil which was purified by flash chromatography (50:50 CH2 Cl2 /petroleum ether) to give a colorless oil (19.70 g, 80%). NMR (CDCl3) delta 3.30 (s, 2H. ArCH), 3.50 (s, 3H, OCH3), 3.65-3.85 (m, 2H, OCH2), 4.00-4.25 (m, 2H, OCH2), 6.85-7.40 (m, 9H, ArH). This procedure produces (Z)-1,1-Dichloro-2-[4-(-methoxyethoxy)phenyl]-3-phenylcyclopropane. | |
With sodium hydroxide; In chloroform; | To (Z)-1-[4-(2-methoxyethoxy)phenyl]-2-phenylethylene (15.61 g, 0.06 mol) dissolved in CHCl3 (193 mL) was added triethylbenzyl-ammonium chloride (0.98 g, 0.004 mol), chilled 40% NaOH solution (96.00 g, 2.40 mol) was added slowly through a dropping funnel according to the method of Dehmlow and Schonefeld, J. Liebiqs Ann Chem. 744:42 (1971) and the mixture stirred for 80 h. The resulting brown emulsion was poured onto 200 mL water in a separatory funnel and the layers were separated, the aqueous layer was extracted with three 50 mL portions of CH2 Cl2, the combined organic extracts were washed with brine, dried over MgSO4, filtered and evaporated in vacuo to obtain a dark brown oil which was purified by flash chromatography (50:50 CH2 Cl2 /petroleum ether) to give a colorless oil (19.70 g, 80%). NMR (CDCl3) delta 3.30 (s, 2H, ArCH), 3.50 (s, 3H, OCH3), 3.65-3.85 (m, 2H, OCH2), 4.00-4.25 (m, 2H, OCH2), 6.85-7.40 (m, 9H, ArH). This procedure produces (Z)-1,1-Dichloro-2-[4-(2-methoxyethoxy)phenyl]-3-phenylcyclopropane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With sodium hydrogencarbonate; In dichloromethane; water; | EXAMPLE 3 This Example illustrates the preparation of methyl(E)-2-[2-(6-chloro-2H-benzo[1,4]oxazin-3-yloxymethyl)phenyl]-3-methoxypropenoate. (Compound No. 2 of Table 1). Chloroacetyl chloride (2.39 ml) in dichloromethane (25 ml) was added to a mixture of 5-chloro-2-hydroxyaniline (3.59 g), triethyl benzylammonium chloride (5.7 g) and sodium bicarbonate (8.4 g) in dichloromethane (100 ml) at 0C. After the addition the mixture was heated to reflux for 4 hours, then cooled and concentrated. The residue was treated with water and the resultant solid washed with ether to give 6-chloro-benzo[1,4]oxazin-3-one (4.2 g, 93% yield) as a buff coloured solid; 1 H NMR (270 Mz): 3.2(1H,brd), 4.42(2H,s), 6.8-7.0(3H,m) ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
14 parts (52.7%) | With sodium hydroxide; In dichloromethane; water; | EXAMPLE 3 To a stirred mixture of 0.5 parts of N,N,N-triethylbenzenemethanaminium chloride, 4 parts of sodium hydroxide and 40 parts of water were added dropwise 16 parts of <strong>[18113-03-6]2-chloro-4-methoxyphenol</strong> and 18.2 parts of 1,2-dibromoethane at 50 C. Upon complete addition, stirring was continued overnight at 50 C. The reaction mixture was poured into water and the product was extracted with a mixture of 2,2'-oxybispropane and dichloromethane. The extract was dried, filtered and evaporated, yielding 14 parts (52.7%) of 1-(2-bromoethoxy)-2-chloro-4-methoxybenzene as a residue (int. 5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water; toluene | 1 EXAMPLE 1 EXAMPLE 1 8.28 g. (0.0495 mole) of (+-)-N-methyl-[2-(4-fluoro-phenyl)-1-methyl]-ethyl amine (J. Am. Chem. Soc. 68 1009-1011) are dissolved in 45 ml. of toluene. To the solution 0.078 g. of benzyl triethyl ammonium chloride are added and parallelly 6.48 g. (0.0545 mole) of propargyl bromide and a solution of 2.17 g. (0.0543 mole) of sodium hydroxide in 7.5 ml. of water are added dropwise under stirring within 5 minutes. The temperature of the reaction mixture rises from 23° C. to 26° C. The reaction mixture is stirred at 26°-28° C. for 20 hours whereupon the two phases are separated, the toluene layer is dried over anhydrous sodium sulfate and evaporated. The residue is distilled at 80°-82° C./0.1 Hgmm. Thus 5.05 g. of (+-)-N-methyl-N-propynyl-[2-(4-fluoro-phenyl)-1-methyl]-ethyl amine are obtained, nD20 =1.5050. The hydrochloride melts at 132°-133° |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; ammonium hydroxide; thionyl chloride; sodium methylate; acetic anhydride; In pyridine; methanol; 1,1,2-trichloroethane; water; | Example 18 preparation of sucralose The product of Example 8 was washed sequentially with toluene, methanol and ether to remove most of the pyridine hydrochloride, then dried in vacuo at room temperature for 2 hours. To a portion of the dry sucrose 6-acetate persulphite (10 g), in 1,1,2-trichloroethane (40 ml), was added thionyl chloride (5 ml: 3.5ME), followed by BETEC (0.9 g; 0.2ME). The reaction mixture was heated slowly to reflux (112 C.) and held at reflux for 1.5 hours, then cooled to room temperature. To the cooled mixture was added ammonium hydroxide solution (0.880 SG, 6 ml) and water (12 ml) and the mixture was stirred vigorously for 3 hours at room temperature. Concentrated hydrochloric acid was then added slowly to neutralise the mixture, which was then concentrated to a syrupy residue by evaporation. The syrup was then acetylated in the conventional manner, with acetic anhydride in pyridine. Sucralose pentaacetate (TOSPA) was separated from the reaction mixture by crystallisation, taken up in methanol and deacetylated by treatment with sodium methoxide in the conventional manner, to yield sucralose (2.1 g). |
Yield | Reaction Conditions | Operation in experiment |
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With sodium hydroxide; In chloroform; | Stage 2: 4-[(2,2-dichlorocyclopropyl)methyl]-2,3,5,6-tetrafluorobenzyl tetrahydropyran-2-yl ether 4-[prop-2-en-1-yl]-2,3,5,6-tetrafluorobenzyl tetrahydropyran-2-yl ether (1.0 q) was treated with aqueous sodium hydroxide (10 cm3; 40% w/v) and benzyltriethyl ammonium chloride (0.050 g; phase transfer catalyst). To the rapidly stirred mixture was added chloroform (5 cm3, ethanol free) and the reaction heated at the reflux temperature for 6 hours. The reaction mixture was cooled to the ambient temperature, diluted with dichloromethane (100 cm3) and water (100 cm3). The organic fraction was separated, washed with water (50 cm3) and dried (anhydrous magnesium sulphate). The solvent was evaporated under reduced pressure to yield a brown oil which was fractionated by chromatography on silica gel eluted with n-hexane/ethyl acetate (25:1 by volume). The title product (0.44 g) was obtained as a colourless oil. 1 H NMR (CDCl3): 1.2-1.35 (t,1H); 1.45-2.00 (m;8H); 2.70- 2.85 (m;1H); 3.15-3.30 (m;1H); 3.45-3.65 (m,1H) 3.85-4.0 (m,1H); 4.50-4.60 (m,1H); 4.70-4.90 (m,2H); | |
With sodium hydroxide; In chloroform; | Stage 2 : 4-[(2,2-dichlorocyclopropyl)methyl]-2,3,5,6-tetrafluorobenzyl tetrahydropyran-2-yl ether 4-[prop-2-en-1-yl]-2,3,5,6-tetrafluorobenzyl tetrahydropyran-2-yl ether (1.0 g) was treated with aqueous sodium hydroxide (10 cm3; 40% w/v) and benzyltriethyl ammonium chloride (0.050 g; phase transfer catalyst). To the rapidly stirred mixture was added chloroform (5 cm3, ethanol free) and the reaction heated at the reflux temperature for 6 hours. The reaction mixture was cooled to the ambient temperature, diluted with dichloromethane (100 cm3) and water (100 cm3). The organic fraction was separated, washed with water (50 cm3) and dried (anhydrous magnesium sulphate). The solvent was evaporated under reduced pressure to yield a brown oil which was fractionated by chromatography on silica gel eluted with n -hexane/ethyl acetate (25:1 by volume). The title product (0.44 g) was obtained as a colourless oil. 1H NMR (CDCl3): 1.2-1.35 (t,1H); 1.45-2.00 (m;8H); 2.70-2.85 (m;1H); 3.15-3.30 (m;1H); 3.45-3.65 (m,1H) 3.85-4.0 (m,1H); 4.50-4.60 (m,1H); 4.70-4.90 (m,2H); GLC Retention Time: 7.90 minutes |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In chloroform; | (a) Preparation of p-benziloxy Mandelic Acid 4-benziloxy benzaldehyde (21.2 g; 0.1 moles) was dissolved in 16 ml of CHCl3. To the solution, 1.14 g of triethyl benzylammonium chloride and 25 ml of 50% NaOH were added. The reaction mixture was kept at 60 C. for 1 hour. The phases were separated. The aqueous phase was washed with ethyl ether, acidified with 50% H2 SO4 and repeadetly extracted with ethyl ether. The organic phase, after being washed with H2 O, was concentrated under vacuum, 11.6 g of the title product were obtained, which were crystallized from toluene. | |
With sodium hydroxide; In chloroform; | (a) Preparation of p-benziloxy mandelic acid. 4-benziloxy benzaldehyde (21.2 g; 0.1 moles) was dissolved in 16 ml of CHCl3. To the solution, 1.14 g of triethyl benzylammonium chloride and 25 ml of 50% NaOH were added. The reaction mixture was kept at 60C for 1 hour. The phases were separated. The aqueous phase was washed with ethyl ether, acidified with 50% H2SO4 and repeadetly extracted with ethyl ether. The organic phase, after being washed with H2O,was concentrated under vacuum, 11.6 g of the title product were obtained, which were crystallized from toluene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; | EXAMPLE IV To a stirred mixture of 47 parts of <strong>[1849-01-0]<strong>[1849-01-0]1,3-dihydro-1-methyl-2H-benzimidazol-2-on</strong>e</strong>, 5 parts of N,N,N-triethylbenzenemethanaminium chloride and 375 parts of a sodium hydroxide solution 50% are added 96 parts of 1-bromo-3-chloropropane at 60 C. The whole is heated to 70 C. and stirring is continued for 1 hour at 70 C. The reaction mixture is poured onto crushed ice and the product is extracted with methylbenzene. The extract is washed with water, dried, filtered and evaporated, yielding 80 parts of 1-(3-chloropropyl)-1,3-dihydro-3-methyl-2H-benzimidazol-2-one as an oily residue. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76.3% | In polydimethylsiloxane; | EXAMPLE 5 PREPARATION OF BENZYLTRIETHYLAMMONIUM CHLORIDE In the manner described in Example 4, 101 g of triethylamine (1 mole) was dissolved in 200 g of polydimethylsiloxane. 137 g (1 mole) of benzyl chloride was stirred into this solution. After a reaction time of 5 hours at 80 C., a large amount of solid had formed, which was filtered out and washed with methyl ethyl ketone. After drying, 174 g of benzyltriethylammonium chloride was obtained with a purity of 99.4 to 99.5%. The yield was about 76.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63.8 parts (93.3%) | With sodium hydroxide; In tetrahydrofuran; di-isopropyl ether; | Example 3 To a stirred mixture of 45.3 parts of <strong>[20098-48-0]1,2,3-trichloro-5-nitrobenzene</strong>, 300 parts of a sodium hydroxide solution 50%, 5 parts of N,N,N-triethylbenzenemethanaminium chloride and 360 parts of tetrahydrofuran was added dropwise, during a 5 minutes period, a solution of 33.3 parts of 4-chlorobenzeneacetonitrile in 90 parts of tetrahydrofuran. Upon completion, stirring was continued for 4 hours at 50 C. The reaction mixture was poured into 1500 parts of crushed ice and acidified with concentrate hydrochloric acid. The product was extracted with trichloromethane. The extract was dried, filtered and evaporated. The residue was stirred in 2,2'-oxybispropane. The product was filtered off and dried, yielding 63.8 parts (93.3%) of 2,6-dichloro-alpha-(4-chlorophenyl)-4-nitrobenzeneacetonitrile (intermediate 3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28 parts (29%) | With sodium hydroxide; In tetrahydrofuran; water; | Example VI To a stirred and hot solution of 8.5 parts of N,N,N-triethylbenzenemethanaminium chloride, 40 parts of sodium hydroxide and 360 parts of a sodium hydroxide solution 50%, is added dropwise a solution of 72.7 parts of N,N-bis(2-chloroethyl)-4-methylbenzenesulfonamide and 45.5 parts of 2,4-dichlorobenzeneacetonitrile in 90 parts of tetrahydrofuran. Upon completion, stirring is continued for 3 hours at 50 C. The reacton mixture is cooled, 216 parts of methylbenzene and 480 parts of water are added and the layers are separated. The organic phase is washed with water, dried, filtered and evaporated. The residue is crystallized from 2-propanol, yielding 28 parts (29%) of 4-(2,4-dichlorophenyl)-1-(4-methylphenylsulfonyl)-4-piperidinecarbonitrile; mp. 145 C. Following the same procedure and using therein an equivalent amount of an appropriate arylacetonitrile there are also prepared: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.4% | With sodium hydroxide; | EXAMPLE 1 Preparation of <strong>[2424-92-2]octadecane-1,18-dicarboxylic acid</strong> glycidyl ester (Compound 1) Octadecane-1,18-dicarboxylic acid (342 parts), 925 parts of epichlorohydrin and 2 parts of benzyltriethyl ammonium chloride are heated and refluxed at 90 to 100 C. for 30 minutes with stirring for esterification. At the same temperature, 208 parts of 50% aqueous solution of sodium hydroxide is added dropwise to the mixture over a period of 60 minutes. The mixture is further heated with stirring for 15 minutes. When the temperature of the mixture has reached 105 C., the mixture is cooled to room temperature and filtered to remove sodium chloride. The epichlorohydrin is recovered from the filtrate in a vacuum, the residue is dissolved in 1 liter of toluene, and the solution is washed with three 300-ml portions of water. The solution is distilled in a vacuum (1 mm Hg) to completely recover the toluene at 140 C. to obtain <strong>[2424-92-2]octadecane-1,18-dicarboxylic acid</strong> diglycidyl ester. Yield 98.4%, epoxy equivalent weight 240, neutralization value 0.02, saponification value 260.1, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
22% | With sodium hydroxide; In dichloromethane; water; | The product was identified as N-methyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide. EXAMPLE 2 2'-n-butoxy-6'-ethyl-2-chloroacetanilide, 5.4 gms (0.02 mol), diethyl sulfate, 3.4 gms (0.22 mol) and 2.0 gms of triethyl benzyl ammonium chloride were mixed in 150 ml of CH2 Cl2 under cooling. Forty-five (45) ml of 50% NaOH were then added all at once at 18 C. and the mixture stirred for ten minutes. Water (150 ml) was added and the resultant layers separated. The organic layer was washed with water, dried over MgSO4 and evaporated by Kugelrohr. A clear liquid (yellows), b.p. 113 C. at 0.05 mm Hg was obtained in 22% yield (1.3 gms). Anal. Calc'd for C16 H24 ClNO2 (%): C, 64.53; H, 8.12; Cl, 11,90. Found: C, 64.26; H, 8.16; Cl, 11.79 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In dichloromethane; water; | (b) 1.4 g of benzyltriethyl ammoniumchloride (TEBA) and a solution of 12 g of sodium hydroxide in 12 ml of water are added with stirring to a solution of 9.6 g of <strong>[20150-83-8]6-methyl-1,2,3,4-tetrahydroquinolin-2-one</strong> in 150 ml of methylene chloride. After 20 minutes 23.2 g of diethyl sulphate are added slowly dropwise; stirring is effected for 20 hours, the last 4 hours under reflux. Excess diethyl sulphate is decomposed by addition of 100 ml of 4 N sodium hydroxide solution. One acidifies and extracts for several times with methylene chloride. The organic phase is dried and concentrated and the residue is purified by chromatography over silica gel (eluent: methylene chloride). 9.4 g (83% of theory) of 1-ethyl-<strong>[20150-83-8]6-methyl-1,2,3,4-tetrahydroquinolin-2-one</strong> are obtained as oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With sodium hydroxide; In dichloromethane; | EXAMPLE 3 Preparation of N-cyclopentyl-N (1,1,2,2-tetrachloroethylthio)-bromomethanesulfonamide A 5.76 g (0.072 mol) 50% aqueous solution of sodium hydroxide was added slowly to a solution of 8.6 g (0.036 mol) N-cyclopentyl bromomethanesulfonamide, 8.6 g (0.036 mol) 1,1,2,2-tetrachloroethylsulfenyl chloride, and about 0.1 g benzyltriethyl ammonium chloride in 200 mol dichloromethane cooled to 0 C. with an ice bath. The reaction mixture was then stirred at 0 C. for 2 hours, washed with water, dried over magnesium sulfate and evaporated to give a brown oil. The oil was chromatographed over silica gel with dichloromethane/petroleum-ether solution to give 5.5 g (35% yield) of the product, as a grey solid, m.p. 59-60 C. |
35% | With sodium hydroxide; In dichloromethane; | EXAMPLE 2 Preparation of N-cyclopentyl-N (1,1,2,2-tetrachloroethylthio)-bromomethanesulfonamide A 5.76 g (0.072 mol) 50% aqueous solution of sodium hydroxide was added slowly to a solution of 8.6 g (0.036 mol) N-cyclopentyl bromomethanesulfonamide, 8.6 g (0.036 mol) 1,1,2,2-tetrachloroethylsulfenyl chloride, and about 0.1 g benzyltriethyl ammonium chloride in 200 mol dichloromethane cooled to 0 C with an ice bath. The reaction mixture was then stirred at 0 C for 2 hours, washed with water, dried over magnesium sulfate and evaporated to give a brown oil. The oil was chromatography over silica gel with dichloromethane/petroleum-ether elution to give 5.5 g (35% yield) of the product, as a grey solid, m.p. 59-60 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sodium hydroxide; In hexane; dichloromethane; | EXAMPLE 4 Preparation of 2-Chloro-2'-Nitro-N-(Isobutoxymethyl)Acetanilide 6.0 g. of 2'-Nitro-2-chloroacetanilide was mixed with 6 ml. of chloromethyl isobutyl ether and 2 g. benzyltriethyl ammonium chloride (phase transfer catalyst) in 100 ml. of methylene chloride at 25 C. Thereafter, 150 ml. of 10% sodium hydroxide was added in one portion. The mixture was vigorously stirred for 30 minutes at room temperature. The organic/aqueous layers were separated and the methylene chloride layer was washed once with 2.5% sodium chloride. The sodium chloride solution was removed and the methylene chloride portion was vacuum treated to remove solvent. The residue was vacuum distilled through a Kugelrohr to give an orange oil, containing a trace of starting material. The residue was eluted through a silica gel wet column with 3:2 hexane/ether as eluant. The product was recovered as a yellow oil from the second fraction, and it distilled at 155-165 C. (0.4 mm Hg) to give 5.1 g. (66% yield) of yellow oil identified as 2-chloro-2'-nitro-N-(isobutoxymethyl)acetanilide. Anal. Calc'd. for C13 H17 ClN2 O4: C, 51.92; H, 5.70; N, 9.31; Found: C, 52.62; H, 5.83; N, 9.21. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.6% | In sodium hydroxide; water; | EXAMPLE 5 Preparation of 7-methoxy-2,2-dimethyl-4-chromanone In 40 ml of 5% sodium hydroxide solution 3.84 g (20 millimoles) of 7-hydroxy-2,2-dimethyl-4-chromanone are dissolved whereupon 80 ml of dichloro methane and 0.5 g of triethyl benzyl ammonium chloride are added and the mixture is intensively stirred at room temperature for 20 minutes. After addition of 4.25 g (1.9 ml, 30 millimole) of methyl iodide the reaction mixture is stirred for 2 hours. The organic layer is separated, washed twice with 50 ml of water each, dried over sodium sulfate and evaporated. The residue is crystallized from 80% methanol. Thus 3.9 g of the desired compound are obtained, yield 94.6%. Mp.: 77-78 C. PMR (CDCl3): 1.38 (6H, s); 2.6 (2H, s); 3.74 (3H, s); 6.3 (1H, d, J=2 Hz); 6.44 (1H, dd, J=8 Hz, respectively J=2 Hz); 7.7 (1H, d, J=8 Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In sodium hydroxide; water; | EXAMPLE 27 Preparation of 6-methoxy-7-sec. butoxy-2,2-dimethyl-4-chromanone In 40 ml of a 5% sodium hydroxide solution 5.2 g (20 millimoles) of 6-hydroxy-7-sec. butoxy-2,2-dimethyl-4-chromanone are dissolved whereupon 80 ml of dichloro methane and 0.5 g of triethyl benzyl ammonium chloride are added and the mixture is intensively stirred at room temperature for 30 minutes. After the addition of 4.25 g (1.9 ml, 30 millimoles) of methyl iodide the reaction mixture is stirred for further 2 hours. The organic phase is separated, washed twice with 50 ml of water each, dried over sodium sulfate and the solvent is removed. The residue is crystallized from 90% ethanol. Thus 5.34 g of the desired compound are obtained, yield 96%. Mp.: 92.5-93 C. PMR (CDCl3): 0.96 (3H, t, J=6 Hz); 1.34 (3H, d, J=4 Hz); 1.4 (6H, s); 1.7 (2H, m); 2.6 (2H, s); 3.8 (3H, s); 4.3 (1H, m); 6.36 (1H, s); 7.22 (1H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In chloroform | 1.B B. B. 2,2-Dichloro-1-methyl-cyclopropanecarboxylic acid 4 g (0.0176 mol) of benzyltriethyl-ammonium chloride are added to 102 ml of 50% strength sodium hydroxide solution (1.27 mols). 50 g (0.5 mol) of methyl acrylate and 119.5 g (1.0 mol) of chloroform are added while stirring at a speed of 500-600 revolutions/minute and cooling to 5°-10° C. The reaction mixture is stirred for 24 hours at 20°-25° C, then diluted with cold water (500 ml) and extracted four times with 150 ml of petroleum ether and ether. The aqueous phase is acidified by means of concentrated HCl and extracted with chloroform/methyl ethyl ketone, and the extracts are dried over Ha2 SO4. The end product is isolated by vacuum distillation. Boiling point (0.25 mm.Hg): 76° C Yield: 37.5 g (44.4%) C5 H6 Cl2 O2 (169.013) Calculated: C, 35.54; H, 3,58; Cl, 41.96%. Found: C, 34.9; H, 3.6; Cl, 42.0%. NMR signals at δ (solvent CDCl3): 1.4 (1H); 1.55-1.7 (3H); 2.3-2.4 (1H); 12.1 ppm (1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9.7 parts (60.3%) | With sodium hydroxide; sodium formate;palladium on charcoal; In water; | EXAMPLE 2 To a solution of sodium formate (38 parts) in water (100 parts) are added sodium hydroxide liquor (32percent; 13.5 parts), benzyl triethylammonium chloride (1.0 parts), 3percent palladium on charcoal (50percent paste; 6.0 parts) and 5-chloro-2-aminobenzotrifluoride (19.6 parts). The mixture is stirred rapidly at the boil under reflux for 4 hours and then steam distilled. The distillate is extracted with chloroform (2 * 50 parts), the extract dried over magnesium sulphate and then the solvent removed to give 9.7 parts (60.3percent) of 2-aminobenzotrifluoride. When the above procedure is repeated in absence of benzyltriethylammonium chloride the yield of 2-aminobenzotrifluoride falls to 23percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.0% | In water; | EXAMPLE 6 129.5 grams of bromochloromethane were treated with 76 grams of ammonium thiocyanate dissolved in 100 grams of water. With addition of 4 grams of benzyl triethyl ammonium chloride the mixture was boiled at reflux for 5 hours. The organic phase was washed with water and distilled in a vacuum. There were isolated 76.4 grams of chloromethyl thiocyanate, corresponding to a yield of 71.0% of theory. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.5% | In water; | EXAMPLE 7 129.5 grams (1 mole) of bromochloromethane were dissolved in 100 grams of water with 105.2 grams (0.5 mole) of calcium thiocyanate trihydrate and treated with 4 grams of benzyl triethyl ammonium chloride. The mixture was boiled at reflux with stirring for 10 hours. The organic phase was washed with water and distilled in a vacuum. There were isolated 78.0 grams of chloromethyl thiocyanate, corresponding to a yield of 72.5% of theory. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water; | EXAMPLE V To a stirred and hot (50 C.) mixture of 28.3 parts of <strong>[52099-72-6]1,3-dihydro-1-(1-methylethenyl)-2H-benzimidazol-2-one</strong>, 5 parts of N,N,N-triethylbenzenemethanaminium chloride and 225 parts of a sodium hydroxide solution 60% are added dropwise, during a 30 minutes-period, 33.7 parts of 1-bromo-4-chlorobutane. Upon completion, stirring is continued for 5 hours at 60 C. The reaction mixture is cooled, water is added and the product is extracted with methylbenzene. The extract is dried, filtered and evaporated, yielding 1-(4-chlorobutyl)-1,3-dihydro-3-(1-methylethenyl)-2H-benzimidazol-2-one as a residue. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81.1% | With sodium hydroxide; In dichloromethane; water; | Example 6 5-Methoxy-2-[(3,5-dimethyl-4-nitro-2-pyridinyl)methylthio]-1H-benzimidazole (IX) Method-A To a suspension of 5-methyl-2-mercaptobenzimidazole (36 gm, 0.2 mole), 2-Chloromethyl-3,5-dimethyl-4-nitropyridine hydrochloride (VII) (47.4 gm, 0.2 mole) and triethyl benzylammonium chloride (5 gm) in a dichloromethane (500 ml) was added dropwise a solution of NaOH (17.6 gm, 0.44 mole) in water (30 ml). The addition was exothermic and the temperature was observed to rise to 40 C. with reflux of dichloromethane-the reaction mixture was stirred for further 6 hours at ambient temperature and filtered. The cake was washed with water and dried in vacuum oven to yield 55.8 gm of cream color product. Yield 81.1% gm; Melting Point 124-128 C.; 1H NMR (in CDCl3), 2.34 (s, 3H), 2.38 (s, 3H), 3.83 (s, 3H) 4.51 (s, 2H), 6.86 (dd, J-9 Hz, 13 Hz, 1H), 7.21 (d, J-13 Hz, 1H), 7.57 (d, J-9 Hz, I H), 8.51 (s, 1H), 11.2 (s, exchange with D2O, 1H). |
Yield | Reaction Conditions | Operation in experiment |
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With potassium permanganate; sodium sulfate; In water; 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; | (iv) 4-(4-Nitro-phenyl)-morpholin-3-one To a solution of 10 g 4-(4-Nitro-phenyl)-morpholine in 200 ml DCM, 32 g Benzyl-triethylammonium chloride and 22.7 g potassium permanganate (325 mesh) were cautiously added at RT. After stirring for 1 h at RT the reaction mixture was heated to reflux for 10 h. Then a solution of 95 g Na2SO3 in 450 ml water were added under ice cooling and vigourous stirring. The mixture was filtered trough a pad of celite and the filtrate was concentrated under reduced pressure. The yellow solid was stirred with 250 ml water and the precipitated product was collected by filtration. This crude product was purified by chromatography on silica gel eluding with a gradient of DCM/MeOH 100%->50%. The fractions containing the product were combined and the solvent evaporated under reduced pressure. Yield: 2.6 g. |
Yield | Reaction Conditions | Operation in experiment |
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91% | With potassium carbonate; paraformaldehyde; In cyclohexane; water; | (g) Methyl 2-[7-bromo-2-(methyloxy)-8-quinolinyl]-2-propenoate A mixture of methyl [7-bromo-2-(methyloxy)-8-quinolinyl]acetate (13.1 g; 42.2 mol), paraformaldehyde (8.8 g; 295 mmol), potassium carbonate (5.8 g; 63 mmol) and benzyltriethyl ammonium chloride (15.4 g; 67.6 mmol) in cyclohexane (275 ml) was heated at 85C, with vigorous stirring for 18 hours. More paraformaldehyde (8.8 g; 295 mmol), potassium carbonate (2.9 g; 29.5 mmol) and benzyltriethyl ammonium chloride (7.7 g; 33.8 mmol) were added and the reaction mixture was stirred at 85 C for a further 5 hours and then at 90 C for 18 hours. The mixture was cooled, water (200 ml) added and the mixture was extracted with ethyl acetate (2x 200 ml). The combined organic layers were washed with brine (150 ml), dried over magnesium sulphate and evaporated under vacuum affording a white solid (12.4 g, 91%). MS (+ve ion electrospray) m/z 323 (MH+). |
Yield | Reaction Conditions | Operation in experiment |
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With sodium hydroxide; In chloroform; water; at 0 - 20℃; for 72.0h; | Example 35:20 Intermediate 9 <n="251"/>[0562] Aqueous NaOH (50%, 30 mL) was added in several portions to a cooled solution of compound 20 (5 g, 7.6 mmol) and BTEAc( benzyl triethyl ammonium chloride) (1.2 g, 6.2 mmol) in chloroform (30 mL) at 0 to 5 C. The vessel was sealed and allowed to stir for 3 days at ambient temperature. The reaction mixture was diluted with H2O and extracted with DCM for three times. The combined organics was concentrated in vacuo and purified by P-HPLC (acidic column) to give 0.65 g of compound ester. NaOH (0.3 g, 7.5 mmol) was added the solution of the ester ( 0.3 g, 0.4 mmol) in 10 mL of EtOH and 3 mL of H2O and stirred for 20 h at rt.[0563] The reaction mixture was concentrated in vacuo and acidified to PH = 3-4 with diluted HCl at 0 C and extracted with ethyl acetate. The organics was dried over Na2SO4 and concentrated to afford 0.2 g of Intermediate 9 as a white solid (yield 11.6%). 1H NMR (400 MHz, DMSO-?6) d 8.59 (s, 1H), 7.31 (q, J=7.6Hz), 7.16 (d, J = 7.6 Hz, 1H), 7.06 (t, 8.4 Hz, 1H), 6.97 (br, 1H). 5.23 (s, 1H) 4.33 (br, 1H), 4.17 (t, J = 7.6 Hz), 3.85 (br, 1H), 2.2 (br, 1H), 2.08 (m, 1H), 1.96 (t, J=08.8 Hz) 1.62 (br, 4 H), 3.48-1.22 (br, 1 1 H), 1.05 (d, 14.8 Hz, 9 H). LC-MS: purity: 96.2%, MS : m/e 733 (M+Na+), 611 ( M-Boc+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | In an open system, 22.8 g (100 mmol) of benzyltriethylammonium chloride and 7.6 g (50 mmol) of sodium bromide were added with 160 ml of ion-exchanged water, and stirred until the compounds were dissolved. Then, 100 ml of dichloromethane was added thereto, and the resultant mixture was vigorously stirred to mix the aqueous phase and organic phase. Subsequently, the mixture was cooled to 0 C., and added dropwise with 40.8 ml (350 mmol) of 47% hydrobromic acid in 15 minutes using a dropping funnel. After the resultant was stirred, the organic phase and the aqueous phase were separated, and the aqueous phase was extracted three times with 40 ml of dichloromethane. Thereafter, the organic phase thus obtained was dried with anhydrous magnesium sulfate, and concentrated to recrystallize the residual solid by using a solvent of dichloromethane and diethyl ether with a volumetric ratio of 5:1. Thereby, BTEABr3 was obtained (an orange crystal: a yield of 37.1 g and 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With aluminum (III) chloride; In dichloromethane; at 5 - 20℃; for 12.5h;Inert atmosphere; | Intermediate 1; Preparation of benzyltriethylammonium chloride.; AlCl3, N= 0.5 (Dl)To a dry two-necked roundbottom flask with a stopper and septum was added benzyltriethylammonium chloride (2.27g, lOmmol) with stirring while maintaining the flask under inert atmosphere by purging with nitrogen. Dichloromethane (25 ml) was added with gentle stirring. When all the benzyltriethylammonium chloride was dissolved completely, the flask was cooled (5-100C) and anhydrous aluminium chloride granules (1.33 g, lOmmol) were added while maintaining the reaction flask under nitrogen. The reaction mixture was stirred under nitrogen for 30 min (5- 100C) and then allowed to stir at room temperature for 12 h .The resultant reaction mixture on careful evaporation furnished a white solid, which was further dried under high vacuum for 6 h. The solid was transferred to an airtight container and should be stored in desiccators.Yield: 3.50 g (97%); NMR in CD2Cl2: 1H delta 7.45-7.60 (m, 5H, Ar), 4.35 (s, 2H, -CHa-Ph), 3.21-3.27 (q, 6H, 3-N-CH2-CH3, J = 7.18Hz) , 1.46- 1.50 (t, 9H, 3-N-CH2-CH1, J = 7.04Hz) ; 13C delta 132.87, 132.19, 132.19, 130.70, 126.52, 61.85, 53.67, 8.75; 27Al delta 103.11. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.2% | In acetonitrile; at 20℃; for 1.0h; | Example 2; Benzyltriethylammonium tris(pentafluoroethyl)difluorochlorophosphate; A mixture of 11.45 g (50.3 mmol) of benzyltriethylammonium chloride and 23.6 g (55.4 mmol) of tris(pentafluoroethyl)difluorophosphorane is dissolved in 30 ml of acetonitrile, and the mixture is stirred at room temperature for one hour. Volatile constituents (excesses of tris(pentafluoroethyl)difluorophosphorane and acetonitrile) are removed in vacuo, and the residue is dried in vacuo for two hours at 7 Pa and at 40-50 C. (temperature of the oil bath). 32.3 g of a viscous, oily material are obtained. The yield of benzyltriethylammonium tris(pentafluoroethyl)difluorochlorophosphate is 98.2%, based on the benzyltriethylammonium chloride employed. The compound is analysed by NMR spectroscopy.NMR data:1H NMR spectrum, ppm: 1.34 t,t (3CH3), 3.14 q (3CH2), 4.30 S(CH2), 7.44-7.58 m (C6H5); J3H,H=7.3 Hz.19F NMR spectrum, ppm: -25.52 d,m (PF), -69.81 d,m (PF), -77.47 t (CF3), -80.03 m (2CF3), -105.11 d,d (CF2, FA), -105.85 d,d (CF2, FB), -108.87 d,m (CF2), -114.72 d,m (CF2, FA), -115.45 d,m (CF2, FB), J1P,F=928 Hz, J1P,F=861 Hz, J2P,F=99 Hz, J2P,F=82 Hz, J2P,F=116 Hz, J2A,B=280 Hz, J4F,F=21 Hz. 31P NMR spectrum, ppm: -147.4 d,d,m. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With diethylene glycol dimethyl ether; potassium carbonate at 155℃; for 6h; optical yield given as %de; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | palladium-carbon; In tetrahydrofuran; water; toluene; | Example 2-5 2-Methyl-2-[(4-{(1E)-3-[2-(4-methylbenzoyl)-1H-pyrrol-1-yl]prop-1-en-1-yl}benzyl)oxy]propanoic acid 10 % Palladium carbon (1.40 g, 0.656 mmol, containing 50 % water) was added to a suspension of Example 2-4 (14.0 g, 43.7 mmol), a solution of Example 2-2 in toluene (20.4 g, 53.2 %, 48.1 mmol), benzyltriethyl ammonium chloride (10.0 g, 43.7 mmol) and dicyclohexylmethylamine (12.8 g, 65.6 mmol) in toluene, and the temperature was maintained at 60 C. After the reaction was completed, toluene and THF was added to the mixture, and the mixture was filtrated. To the filtrate was added 10 % aqueous potassium hydroxide solution and THF, and the mixture was partitioned into two layers. The aqueous layer was acidified with aqueous hydrochloric acid, and extracted with toluene, and the toluene layer was further washed with water. The combined organic layer was treated with active carbon and then concentrated, and the concentrated residue was crystallized from toluene/n-heptane. The precipitated crystal was collected through a filter, and the resultant crystal was recrystallized from acetone/water to prepare the title compound (14.0 g, 78 %). 1H NMR (CDCl3, 400 MHz) delta 7.73 (d, 2H, J = 8.0 Hz), 7.40-7.20 (m, 6H), 7.05 (dd, 1H, J = 2.4, 1.7 Hz), 6.77 (dd, 1H, J = 4.0, 1.7 Hz), 6.51 (d, 1H, J = 16.0Hz) , 6.45 (dt, 1H, J = 16.0, 5.0Hz), 6.21 (dd, 1H, J = 4.0, 2.4 Hz), 5.20 (d, 2H, J = 5.0 Hz), 4.49 (s, 2H), 2.42 (s, 3H), 1.56 (s, 6H), MS(ESI): m/z 418 (M+1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In dichloromethane for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water; 1,2-dichloro-ethane; at 45 - 55℃; for 3.75h;Inert atmosphere; | In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), a mixture of benzyltriethylammonium chloride (18.0 g, 78 mmol) in 50% aqueous NaOH solution (1.2 L) was heated to 45 C. A chilled solution of cyclopentadiene (formed by cracking of cyclopentadiene dimer at 180 C, 140 ml_, 1.70 mol) in 1 ,2- dichloroethane (122 ml_, 1.55 mol) was added to the stirred NaOH solution while keeping the internal temperature below 55 C. After completion of the addition (ca. 1.75 h), the reaction mixture was stirred at 50 C for 2 h and allowed to cool down to rt. The layers were separated, the organic layer washed with 1 M NaOH, dried (Na2S04) and filtered. The crude brown liquid was distilled under reduced pressure (85-95 mbar) and the title compound was obtained as a colorless liquid (bp = 45-50 C at 80 mbar). 1H NM (400 MHz, CDCI3) delta 6.58 (m, 2H), 6.19 (m, 2H), 1.71 (s, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | In dichloromethane; for 6.0h;UV-irradiation; Inert atmosphere; | Carbon monoxide was bubbled through an irradiated solution of [1b]PF6 (71 mg, 0.14 mmol), [Et3NCH2Ph]Cl (37 mg, 0.16 mmol) in CH2Cl2 (5 ml) for 6 h. The solvent was evaporated, the residue was purified by elution through a 5 cm silica gel column first with hexane (to remove naphthalene) and then with a CH2Cl2-hexane (1:1) mixture. The yellow band was collected and dried in vacuo to give 4 (39 mg, 84%). 1H NMR (CDCl3) delta: 1.90 (s, 15 H, Cp*) (cf. ref. 14). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | In dichloromethane;Inert atmosphere; | A solution of [ 1]PF6 (51mg, 0.10mmol), P(OMe)3 (0.1ml, 0.80mmol), and [Et3NBn]Cl (23mg, 0.10mmol) in CH2Cl2 (2ml) was stirred overnight. The solvent was evaporated, the residue was dissolved in CH2Cl2 and eluted through a short alumina column (3cm) with petroleum ether-CH2Cl2 mixture (1:1). Resulting solution was evaporated and the residue was washed with cold pentane (2ml) to give 3a (30mg, 0.058mmol, 58% yield) as yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | In dichloromethane;Inert atmosphere; | A solution of [1]PF6 (51mg, 0.10mmol), dppe (40mg, 0.10mmol), and [Et3NBn]Cl (23mg, 0.10mmol) in CH2Cl2 (2ml) was stirred overnight. The solvent was evaporated and the residue was extracted with Et2O (2×3ml). Yellow extract was evaporated and the residue was washed with cold pentane (2ml) to give 3b (42mg, 0.063mmol, 65% yield) as bright yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | In 1,2-dichloro-ethane; for 1.0h;Inert atmosphere; | General procedure: A mixture of complex 4aPF6 (30mg, 0.06mmol) and [BnNEt3]Cl, [Bu4N]Br or [Bu4N]I (0.08mmol) was stirred in 1ml of 1,2-dichloroethane for 1h. The mixture was centrifuged and the solid precipitate was washed with 1,2-dichloroethane and ether. After drying salts 4aX were obtained as white solids. 4aCl, yield 64%. 1H NMR (CD3CN) delta: 6.60 (s, 6H, C6H6), 5.66 (s, 1H, cage CH), 4.48 (s, 1H, cage CH), 3.84 (s, 2H, 1,2-dichloroethane), 2.63 (s, 3H, SMe2), 2.60 (s, 3H, SMe2). 11B{1H} NMR (CD3CN) delta:-0.08 (1),-0.59 (1),-1.47 (1),-7.57 (1),-8.47 (1B),-12.56 (1),-19.60 (1),-21.20 (1),-24.31 (1). Found (%): C, 30.12; H, 6.02; B, 19.87. Calc. for C10H22B9SRuCl·Cl2C2H4 (%): C, 28.87; H, 5.29; B, 21.26. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With potassium hydroxide; In chloroform; water; | 100 mg (0.26 mmol) of bis-protected bromo-emodin synthesized in Example 2 was dissolved in chloroform,Poured into a 50 mL three-necked flask and added 140 mg (2.5 mmol) of KOH, 5 mL of water, 50 mg of TEBA (benzyltriethylammonium chloride as a phase transfer catalyst), and 0.35 mL of 33% The solution was extracted with 15 mL of chloroform three times. The organic layer was combined and the solvent was removed by steaming. The resulting solid was purified by silica gel column chromatography using dichloromethane-acetone as eluent (64.7 mg, 0.18 mmol), and the product was characterized by the following procedure: & lt; RTI ID = 0.0 & gt; 1: 30: 1 ? 15: 1 ? 10: 1 ? 5: 1 ? 2: 1, The data are as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With dimethyl amine; potassium hydroxide; In chloroform; water; at 20℃; for 4.0h; | 250 mg (0.69 mmol) of bis-drag protected procyanid synthesized in Example 5 was dissolved in chloroform, poured into a 50 mL three-necked flask, and 465 mg (8.30 mmol) of KOH, 5 mL of water, 125 mg of TEBA (benzyltriethyl Ammonium chloride as a phase transfer catalyst) and 0.95 mL of 33% aqueous solution of dimethylamine (6.9 mmol) was added and the reaction was stirred at room temperature for 4 h. After the reaction was completed, the HAc solution was slowly added to adjust the pH to near neutral After extraction with 15 mL of chloroform, the organic layers were combined and the solvent was removed by steaming. The resulting solid was chromatographed on silica gel using dichloromethane-acetone as eluant in a volume ratio of 45: 1 ? 30: 1 ? 15: 1 ? 10: 1 ? 5: 1 ? 3: 1 gradient elution, the double deprotective emodin tertiary amine 3 (192mg, 0.59mmol), the product characterization data are as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 200 mg; 50% | With potassium hydroxide semihydrate; phosphorus; In water; toluene; at 95℃; for 3.0h;Inert atmosphere; | To a suspension of red phosphorus (2.00 g, 65 mmol), powdered KOH 0.5H2O (7.80 g, 120mmol), and TEBAC (0.32 g) in toluene (20 mL), a solution of hydrochloride 2 (1.48 g, 90 mmol) in H2O (4 mL) was added. The reaction mixture was stirred at 95 C for 3 h under argon then cooled to room temperature. The toluene layer was decanted, solvent removed under reduced pressure, and the residue washed with diethyl ether (5x1 mL) before recrystallization from hot hexane to yield phosphine oxide 3 0.49 g (50%). m.p. 135 C (hexane). IR (KBr): 3425,3056, 3000, 2916, 1588, 1471, 1430, 1400, 1306, 1248, 1198, 1153, 1120, 1073,1048, 993, 851, 786, 750, 710, 626, 578, 495 cm1.1H NMR (400.13 MHz,CDCl3): d = 3.48 (d, 2 H,2JPH = 14.8 Hz, PCH2), 7.15 (dd, 1 H,3J5-6 = 4.4;3J5-4 =7.6 Hz, H-5), 7.41 (d, 1 H,3J3-4 = 7.7 Hz, H-3), 7.60 (t, 1 H,3J4-3 = 3J4-5 = 7.6 Hz,H-4), 8.53 (d, 1 H,3J6-5 = 4.4 Hz, H-6).13C NMR (100.62 MHz, CDCl3): d = 38.32(d,1JPC = 60.0 Hz, PCH2), 121.75 (d, C-5), 125.11 (d,3JPC = 4.4 Hz, C-3), 136.60(C-4), 149.40 (C-6), 153.13 (d,2JPC = 7.8 Hz, C-2).31P NMR (161.98 MHz, CDCl3) :d = 42.81 ppm, lit.11d(42.5 ppm).15N NMR (CDCl3): d = 67.7 ppm. Anal.Calcd C18H18N3OP: C, 66.86; H, 5.61; N, 13.0; P, 9.58. Found: C, 66.76; H, 5.68; N,12.92; P, 9.43. From the diethyl ether extracts, the solvent was removed to give 0.03 g of a waxy product; mass spectrometry showed two molecular ion peaks (GCMS): 323.15 (M+) and 322.15 (M+). The first corresponds to phosphine oxide 3, calcd. C18H18N3OP: 323.1187, found 323.15 (M+, 10%), lit.11d(323.1181 (M+,100%), and the second corresponds to di(2-picolyl)benzylphosphine oxide, calcd. C19H19N2OP: 322.12, found 322.15 (M+, 24%) (see also Fig. S9). The 31PNMR spectrum of this product contained two signals: 42.2 ppm (3) and 45.4 ppm [bis(2-picolyl)benzylphosphine oxide]; molar ratio of the compounds1:3. The aqueous-alkaline layer was neutralized to pH 6-7 with H3PO4, then water was removed under reduced pressure, and the solid residue washed with chloroform. The solvent was removed from the extract to give 200 mg of bis(2-pyridylmethyl)ether (see Fig. S6). 2,2?-(Oxybis(methylene))dipyridine: 1HNMR (400.13 MHz, CDCl3): d = 4.76 (s, 2 H, OCH2), 7.17 (d.d, 1 H,3J5-6 = 4.4;3J5-4 = 7.6 Hz, H-5), 7.51 (d, 1 H,3J3-4 = 7.7 Hz, H-3), 7.68 (t, 1 H,3J4-3 = 3J4-5 = 7.6Hz, H-4), 8.54 (d, 1 H,3J6-5 = 4.4 Hz, H-6). X-ray crystallographic data for compound 3: C18H18N3OP, Mr = 323.32, trigonal, space group R3, a = 16.3086(7) A, b = 16.3086(7) A, c = 5.2997(2) A, a = 90, b = 90, c = 120, V = 1220.7(1) A3, Z=3, dcalc = 1.319 g/cm3, m(Mo-Ka) = 0.177 mm1,2H range = 4.99-60.04, independent reflections 1576 (Rint = 0.0496), data/restraints/parameters: 5117/0/70, R indexes: R1 = 0.0474 [I >2r(I)], wR2 (all data) = 0.1135, GOF on F2=1.048. CCDC 1554643 contains the supplementary crystallographic data for this paper. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With sodium hydroxide; In water; toluene; for 2.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With sodium hydroxide; In water; toluene; for 18.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium hydroxide; In water; toluene; for 6.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With sodium hydroxide; In water; toluene; for 17.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With sodium hydroxide; In water; toluene; for 4.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With sodium hydroxide; In water; toluene; for 3.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sodium hydroxide; In water; toluene; for 4.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With sodium hydroxide; In water; toluene; for 8.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With sodium hydroxide; In water; toluene; for 8.0h;Reflux; | General procedure: A 100 mL round-bottom flask was equipped with a magnetic stirbar and a reflux condenser. To xylene (10.0 mL), TEBAC(1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed by a solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of the reaction, the mixture was air-jet cooled to25 C and TLC evidenced the disappearance of the starting material. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sodium hydroxide; In water; toluene; for 2.0h;Reflux; | Using the standard procedure, to xylene (10.0mL), 0.5003 g of TEBAC (1.1 Eq) and 0.2996 g of methanone (a) (1.0 Eq) were added, followed by a solution of NaOH 50% (5.0 mL).The mixture was stirred at reflux temperature for 2 h. After cooling to r.t., TLC revealed the disappearance of the startingmaterial. The reaction mix was treated with AcOEt (4 ×20 mL), and the organic phase separated and removed underreduced pressure. The compound was isolated as an offyellowsolid: 1H NMR: (300MHz, CDCl3) delta = 7.81-7.68 (m,2H), 7.53-7.34 (m, 3H), 7.34-7.10 (m, 5H), 7.00 (t, = 2.1Hz,1H), 6.76 (dd, = 4.1, 1.7Hz, 1H), 6.19 (dd, = 4.1, 2.6Hz,1H), 5.65 (s, 2H). 13C NMR: (126MHz, CDCl3) delta= 186.20,171.26, 139.83, 138.28, 131.46, 130.04, 129.24, 128.62, 128.42,127.34, 127.16, 123.70, 108.73, 69.67, 60.44, 52.37.MS [EI+] m/z (%): 306 (M+), 289 (28), 259 (14), 229 (4), 156 (22), 91 (100),65 (17). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In chloroform; water; at 0 - 20℃; for 17.0h; | To a solution of 5-chloro-2-methyl-1H-indole (5.00 g, 30.3 mmol) and TEBAC (0.60 g, 0.300 mmol) in CHCl3 (150 ml) was added, at 0 C., NaOH in water. The mixture was stirred at 0 C. for 3 h and then at RT for 14 h. The reaction mixture was then added gradually to ice-water and extracted with chloroform. The organic phase was washed with water, dried over Na2SO4 and concentrated on a rotary evaporator. The residue was purified by column chromatography purification with a hexane/ethyl acetate gradient as eluent. MH+: 212; 1H-NMR (400 MHz, CDCl3): delta 2.78 (s, 3H), 7.58-7.61 (dd, J=2.32 & 9.0 Hz, 1H), 7.68-7.69 (d, J=2.28 Hz, 1H), 7.91-7.94 (d, J=9.0 Hz, 1H), 8.01 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In chloroform; water; at 0 - 20℃; for 17h; | To a solution of <strong>[6127-17-9]6-chloro-2-methyl-1H-indole</strong> (5.00 g, 30.3 mmol) and TEBAC (0.60 g, 0.300 mmol) in CHCl3 (150 ml) was added, at 0 C., NaOH in water. The mixture was stirred at 0 C. for 3 h and then at RT for 14 h. The reaction mixture was then added gradually to ice-water and extracted with chloroform. The organic phase was washed with water, dried over Na2SO4 and concentrated on a rotary evaporator. The residue was purified by column chromatography purification with a hexane/ethyl acetate gradient as eluent. MH+: 214; 1H-NMR (400 MHz, CDCl3): delta 2.79 (s, 3H), 7.44-7.47 (dd, J=2.08 & 8.72 Hz, 1H), 7.63-7.65 (d, J=8.72 Hz, 1H), 7.99-8.00 (d, J=1.92 Hz, 1H), 8.07 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65.5% | With sodium hydroxide; In chloroform; at 40 - 50℃; for 5.0h; | 20g benzaldehyde,2g benzyl triethyl ammonium chloride,60g of chloroform was added to the reactor,Warming up to 40 C,Start adding 35% of liquid alkali 100g,Add 2h,Warming up to 50 C,Insulation for 3h,Add 285g of soft water and mix and dilute.After standing for 2 h, the lower layer of chloroform was separated, and the aqueous layer was extracted with 50 g of chloroform. The chloroform layer was separated, and the organic layer was combined to recover chloroform. The aqueous layer was acidified with 25 g of concentrated sulfuric acid. The ethyl ester was extracted three times with water three times, each time 60 g, and distilled under reduced pressure at 50 C to give a crude product. The crude product was added to 60 g of toluene solvent, warmed to 100 C, and kept warm for two hours, slowly dropped to normal temperature, a white solid was precipitated, suction filtered, washed with 90 g of petroleum ether, and dried and weighed. The yield was 18.8 g, the content was 98.6%, and the yield was 65.5%. Fully meet customer needs |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sodium hydroxide; In water; ethylene dibromide; at 0 - 10℃; for 5.0h;Inert atmosphere; | A mixture of TEBAC (505 mg, 2.22 mmol, 0.05 eq ) and aq. NaOH (3.55 g, 44.42 mmol, 100 mL, 50%) were combined with 2-(3-bromo-5-tert-butyl-phenyl)acetonitrile (11.2 g, 44.42 mmol, 1 eq) and l,2-dibromoethane (25.03 g, 133.25 mmol, 10.05 mL, 3 eq) at 0 C. The resulting mixture was stirred at 10 C for 5 hrs. The mixture was poured into ice water (200 mL) and extracted with ethyl acetate (3 x 150 mL). The organic layer was dried over sodium sulfate and concentrated under reduced pressure to give a black brown liquid residue. The residue was purified by flash silica gel chromatography (ISCO; 120 g CombiFlash Silica Flash Column, Eluent of 0~5 % Ethyl acetate/Petroleum ether gradient 80 mL/min). The title compound (9.3 g, 33.43 mmol, 75% yield) was obtained as a yellow solid. NMR (400MHz, CDCL) d = 7.44 (t, J = 1.7 Hz, 1H), 7.32 (t, J = 1.6 Hz, 1H), 7.16 (t, J = 1.7 Hz, 1H), 1.77 - 1.72 (m, 2H), 1.43 - 1.39 (m, 2H), 1.32 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium carbonate In acetone at 20℃; for 3h; | |
80% | With potassium carbonate In acetone at 20℃; for 3h; | Formation of diammonium salt of dithiolate anion(V) A Mixture of coumarin derivative (I) (1.76 g;0.01 mol), anhydrous potassium carbonate (5 g;0.16 mol), benzyl triethyl ammonium chloride (0.5 g;0.01 mol), carbon disulphide (20 mL) in acetone(30 mL) and added different aryl halides namely benzylchloride and/or p-nitro benzyl chloride (0.01 mol)was stirred at room temperature for 3 hours. The solidlayer was separated and washed by dil. HCl (100 mL,10%), dried, crystallized to gives (V) as yellow crystals(chloroform); mp above 350°C; in yield (80%); IR(KBr) cm-1 showed absorption bands at 1690, 1680(C=O) of lactone and ketone; 1H NMR (CDCl3) (ppm): 0.95 (m, 6H, 2CH3), 1.22 (m, 12H, 4CH3),2.34 (s, 3H, CH3), 2.72 (q, 4H, 2CH2-N), 3.42 (q,8H, 4CH2-N), 4.62 (S, 4H, 2CH2-ph), 7.15-8.4 (m,13H, aromatic CH). Anal. calcd. for: C37H50N2O3S2(634.56): C, 69.98, H, 7.93; N, 4.41; Found: C, 70.14;H, 7.81; N, 4.59. |
Tags: 56-37-1 synthesis path| 56-37-1 SDS| 56-37-1 COA| 56-37-1 purity| 56-37-1 application| 56-37-1 NMR| 56-37-1 COA| 56-37-1 structure
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