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[ CAS No. 123944-75-2 ] {[proInfo.proName]}

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Chemical Structure| 123944-75-2
Chemical Structure| 123944-75-2
Structure of 123944-75-2 * Storage: {[proInfo.prStorage]}
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Product Details of [ 123944-75-2 ]

CAS No. :123944-75-2 MDL No. :MFCD11208364
Formula : C9H10ClNO Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 183.64 Pubchem ID :-
Synonyms :

Safety of [ 123944-75-2 ]

Signal Word:Danger Class:8
Precautionary Statements:P264-P270-P271-P280-P303+P361+P353-P304+P340-P305+P351+P338-P310-P330-P331-P363-P403+P233-P501 UN#:3261
Hazard Statements:H302-H314 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 123944-75-2 ]

* 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.

  • Downstream synthetic route of [ 123944-75-2 ]

[ 123944-75-2 ] Synthesis Path-Downstream   1~13

  • 1
  • [ 68319-44-8 ]
  • [ 123944-75-2 ]
  • [ 123944-76-3 ]
YieldReaction ConditionsOperation in experiment
65% With potassium carbonate In N,N-dimethyl-formamide for 60h; Ambient temperature;
  • 2
  • [ 63024-77-1 ]
  • [ 74-89-5 ]
  • [ 123944-75-2 ]
YieldReaction ConditionsOperation in experiment
45% With triethylamine In dichloromethane; water at 0 - 20℃; for 1.16667h;
With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; for 1h;
In tetrahydrofuran; dichloromethane at -10℃; for 0.5h; General procedure: To a mixture of 3-(chloromethyl)benzoic acid (1.7 g, 9.965 mmol, 1.0 eq) in DCM (50 mL) was added (COCl)2 (1.7 mL, 19.931 mmol, 2.0 eq) drop wise at 0° C. The mixture was stirred for 1 h while the solution became clarified. Then the mixture was concentrated under reduced pressure. To a mixture of the residue in DCM was added a solution of NH3 in THF at -10° C. The mixture was stirred for 0.5 h and then concentrated under reduced pressure to give compound PI-28a (1.3 g, 77%)
  • 3
  • [ 123944-75-2 ]
  • [ 220880-22-8 ]
YieldReaction ConditionsOperation in experiment
79.5% With chloro-trimethyl-silane; thionyl chloride In hexane; water; ethyl acetate; toluene; acetonitrile c Preparation of 3-(1-Methyltetrazol-5-yl)benzyl Chloride c. Preparation of 3-(1-methyltetrazol-5-yl)benzyl chloride. A 250 mL round bottom flask equipped with a magnetic stirrer, reflux condenser and calcium chloride drying tube was charged with 27.2 g (148 mmol) of 3-(chloromethyl)-N-methylbenzamide, 100 mL of toluene (dried over molecular sieves 4A). To this solution was added 16.2 mL (222 mmol) of thionyl chloride and the mixture was heated to 85-90° C. for 15 h (Note 6). While heating, evolution of gas, presumably hydrogen chloride and sulfur dioxide, was observed. After cooling to room temperature, excess thionyl chloride and toluene were removed under vacuum. The resulting residue was azeotroped with 100 mL of toluene, then dried under high vacuum for 1 h to give the crude imidoyl chloride. A 500 mL, three necked, round bottom flask equipped with a magnetic stirrer, thermometer and argon bubbler was charged with 11.6 g (178 mmol) of sodium azide and 140 mL of acetonitrile (freshly opened bottle). To this suspension was added 23.7 mL (187 mmol) of chlorotrimethylsilane and the mixture was stirred for 1.5 h at room temperature. After cooling to 0° C., a solution of the crude imidoyl chloride, prepared above, in 40 mL of acetonitrile was added. This heterogeneous mixture was stirred for 1-2 h at 0° C., then allowed to warm to room temperature and stirred for 15 h. TLC analysis indicated complete reaction. The reaction mixture was quenched by the addition of 150 mL of water, then diluted with 150 mL of ethyl acetate. The two layers were separated and the aqueous phase was extracted with 2*100 mL of ethyl acetate. The combined organic layers were washed successively with 200 mL of water, and 200 mL of saturated sodium chloride solution. After drying over anhydrous magnesium sulfate, the solution was concentrated. The residue was further dried in vacuo to give a light yellow solid (29.7 g). This solid was dissolved in 220 mL of 5.5:4.5 hexane:ethyl acetate at ~60-70° C. The resultant solution was allowed to cool to room temperature and was seeded with crystals of product, then stored in a refrigerator overnight. The resulting precipitate was collected by filtration and washed with 50 mL of hexane. After drying by suction, 24.5 g (79.5% yield) of 3-(1-methyltetrazol-5-yl)benzyl chloride was obtained as a white amorphous solid, mp 63-65° C.
Stage #1: 3-(chloromethyl)-N-methylbenzamide With thionyl chloride In toluene at 85 - 90℃; for 15h; Stage #2: With chloro-trimethyl-silane; sodium azide In acetonitrile at 0 - 20℃; for 15h;
  • 4
  • [ 899828-10-5 ]
  • [ 123944-75-2 ]
  • <i>N</i>-methyl-3-[2-(pyridin-2-ylamino)-thiazol-5-ylsulfanylmethyl]-benzamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
20% Stage #1: N-(5-thiocyanatothiazol-2-yl)pyridin-2-amine With sodium tetrahydroborate In tetrahydrofuran; ethanol for 0.416667h; Stage #2: 3-(chloromethyl)-N-methylbenzamide In tetrahydrofuran; ethanol for 2h;
  • 5
  • [ 31719-77-4 ]
  • [ 123944-75-2 ]
YieldReaction ConditionsOperation in experiment
80% With methylamine hydrochloride; N-ethyl-N,N-diisopropylamine In hexane; dichloromethane; water; toluene b Preparation of 3-(1-Methyltetrazol-5-yl)benzyl Chloride b. Preparation of 3-(chloromethyl)-N-methylbenzamide. A 250 mL, round bottom flask equipped with a magnetic stirrer, reflux condenser and calcium chloride drying tube was charged with 34.1 g (200 mmol) of 3-chloromethylbenzoic acid and 125 mL of toluene (dried over molecular sieves 4A). To this suspension was added 21.9 mL (300 mmol) of thoinyl chloride and the mixture was heated to 85-90° C. for 15 h. While heating, evolution of gas, presumably hydrogen chloride and sulfur dioxide, was observed. The reaction mixture was cooled to room temperature and excess thionyl chloride and toluene were removed under vacuum. The resulting oily residue was azeotroped with 100 mL of toluene, then dried under high vacuum for 1 h to give the crude acid chloride. A 1 L, three necked, round bottom flask equipped with a magnetic stirrer, addition funnel, thermometer and argon bubbler was charged with the crude acid chloride obtained above, and 400 mL of dichloromethane (dried over molecular sieves 4A). After the solution was cooled to -5 to 0° C. (using an ice-sodium chloride bath), 14.9 g (220 mmol) of methylamine hydrochloride was added in one portion. To this mixture was added 69.6 mL (400 mmol) of diisopropylethylamine (DIPEA) dropwise over 15-20 min, while maintaining the temperature of the reaction mixture below 2° C. After completion of the addition, the mixture was stirred for 45 min at 0 to 5° C., then allowed to warm to room temperature. After stirring for 15 min at room temperature, TLC analysis indicated complete reaction. The reaction mixture was diluted with 250 mL of water, and stirred for 5 minutes. The two layers were separated and the aqueous phase was extracted with 2*100 mL of dichloromethane. The combined organic layers were washed successively with 300 mL of water, and 300 mL of saturated sodium chloride solution. After drying over anhydrous magnesium sulfate, the solution was concentrated by rotary evaporation under house vacuum. The residue was further dried in vacuo to give a light yellow solid. This solid was dissolved in 110 mL of toluene at ~60-70° C. The resulting solution was allowed to cool to room temperature and seeded with crystals of product, then stored in a refrigerator overnight. The resulting precipitate was collected by filtration and washed with 30 mL of hexane. After drying under high vacuum 29.4 g (80.0% yield) of 3-(chloromethyl)-N-methylbenzamide was obtained as a light yellow solid; mp 59-61° C.
Multi-step reaction with 2 steps 1: SOCl2 / toluene / 15 h / 85 - 90 °C 2: DIPEA / CH2Cl2 / 1 h / 0 - 20 °C
Multi-step reaction with 2 steps 1: oxalyl dichloride / dichloromethane / 1 h / 0 °C 2: dichloromethane; tetrahydrofuran / 0.5 h / -10 °C
  • 6
  • [ 99-04-7 ]
  • [ 123944-75-2 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: NCS; benzoylperoxide / chlorobenzene / 8 h / 95 °C 2: SOCl2 / toluene / 15 h / 85 - 90 °C 3: DIPEA / CH2Cl2 / 1 h / 0 - 20 °C
  • 7
  • [ 123944-75-2 ]
  • 2-{5-[1-(3-methylaminocarbonylbenzyl)-2,5-dioxoimidazolidin-4-ylmethyl]-1H-indol-3-yl}ethylamine [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 65 percent / K2CO3 / dimethylformamide / 60 h / Ambient temperature 2: H2, aq. 2 N HCl / 10percent Pd/C / ethanol; ethyl acetate 3: 1.) aq. HCl, NaNO2, 2.) SnCl2 / 1.) from -5 deg C to 0 deg C, 30 min, 2.) RT, 3 h 4: ethanol; H2O / 2 h / Heating
  • 8
  • [ 123944-75-2 ]
  • 3-[4-(4-Aminobenzyl)-2,5-dioxoimidazolidinylmethyl]-N-methylbenzamide hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 65 percent / K2CO3 / dimethylformamide / 60 h / Ambient temperature 2: H2, aq. 2 N HCl / 10percent Pd/C / ethanol; ethyl acetate
  • 9
  • [ 123944-75-2 ]
  • 3-[4-(4-Hydrazino-benzyl)-2,5-dioxo-imidazolidin-1-ylmethyl]-N-methyl-benzamide; hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 65 percent / K2CO3 / dimethylformamide / 60 h / Ambient temperature 2: H2, aq. 2 N HCl / 10percent Pd/C / ethanol; ethyl acetate 3: 1.) aq. HCl, NaNO2, 2.) SnCl2 / 1.) from -5 deg C to 0 deg C, 30 min, 2.) RT, 3 h
  • 10
  • [ 63024-77-1 ]
  • [ 123944-75-2 ]
YieldReaction ConditionsOperation in experiment
With triethylamine; methylamine In 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran S.1.b (b) (b) 3-Chloromethyl-N-methylbenzamide A solution of 3-chloromethylbenzoyl chloride (7.4 g, Aldrich) in DCM (35 ml) was added dropwise at 0° C. over 30 minutes to a stirred mixture of 30% aqu. methylamine (4.5 ml) and triethylamine (3.6 g) in DCM (50 ml). When addition was complete, the mixture was allowed to warm to room temperature over 1 hour with stirring. Further methylamine (0.5 ml) was added and the mixture stirred for a further 10 minutes, then washed with water, 1N aqu. HCl, 1N aqu. NaOH and brine, dried over MgSO4 and evaporated in vacuo to give the desired product as a colourless oil which solidified to a white solid on standing.
  • 11
  • [ 63024-77-1 ]
  • [ 593-51-1 ]
  • [ 123944-75-2 ]
YieldReaction ConditionsOperation in experiment
With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; To a solution of 3-(chloromethyl)-benzoic acid (34.1 g, 200 mmol) in toluene (125 ml_) was added thionyl chloride (21.9 ml_, 300 mmol) at room temperature. The resulting solution was heated at reflux for 15 hours. The reaction mixture was cooled to room temperature and concentrated under vacuum. The resulting oily residue was azeotroped with toluene and dried under high vacuum to obtain the crude acid chloride. To a suspension of the above crude acid chloride (200 mmol) in dichloromethane (400 ml_) was added methylamine hydrochloride (14.9 g, 220 mmol) at -5 °C to 0 °C. Diisopropylethylamine (69.6 ml_, 400 mmol) was added drop- wise over 15-20 minutes at 0 °C. After completion of the addition, the mixture was stirred for 45 minutes at 0 °C , then warmed to room temperature. After stirring at room temperature for 15 minutes, the reaction mixture was diluted with water (300 ml_) and the aqueous layer was extracted with dichloromethane (100 ml_). The combined organic layers were washed with brine and dried over anhydrous magnesium sulfate. Filtration and concentration gave the crude solid which was dissolved in toluene at -60-70 °C. The resulting solution was stored in the refrigerator overnight and the precipitated solids were collected by filtration and then washed with hexanes. After drying in air, 3-(chloromethyl)-Λ/-methyl-benzamide (80%) was isolated as a light yellow solid.
  • 12
  • [ 123944-75-2 ]
  • C9H9Cl2N [ No CAS ]
YieldReaction ConditionsOperation in experiment
With thionyl chloride In toluene at 20℃; Heating; Reflux; To a suspension of 3-(chloromethyl)-Λ/-methyl-benzamide (27.2 g, 148 mmol) in toluene (100 ml_) was added thionyl chloride (16.2 ml_, 222 mmol) at room temperature. The resulting suspension was heated at reflux for 15 hours. The reaction mixture was cooled to room temperature and then concentrated under vacuum. The residue was azeotroped with toluene and dried under high vacuum. To a suspension of sodium azide (11.6 g, 178 mmol) in acetonitrile (140 ml_) was added chlorotrimethylsilane (23.7 ml_, 187 mmol) at room temperature and the suspension was stirred for 1.5 hours. The reaction mixture was cooled to -10 °C and the above crude imidoyl chloride (148 mmol) in acetonitrile (40 ml_) was added over 5 minutes. The mixture was stirred for 2 hours at 0 °C and then stirred at room temperature for 15 hours. The reaction mixture was diluted with water (200 ml_) and extracted with ethyl acetate (2 X 100 ml_). The combined organic extracts were washed with brine and dried over anhydrous magnesium sulfate. Filtration and concentration gave a light yellow solid which was dissolved in hexanes-ethyl acetate (220 ml_, 11 :9 ratio) at 60-70 °C. The resulting solution was stored in the refrigerator and the precipitated solids were collected by filtration and washed with hexanes. After drying in air, 3-(1 -methyltetrazol-5-yl)benzyl chloride was isolated as 24.5 g (79.5%) of a white amorphous solid, mp 63-65 0C; HRMS (ES+) cald. for C9H9CIN4 [(M+H)+] 209.0589, obsd. 209.0588.
  • 13
  • [ 593-51-1 ]
  • [ 31719-77-4 ]
  • [ 123944-75-2 ]
YieldReaction ConditionsOperation in experiment
98% Stage #1: 3-chloromethylbenzoic acid With thionyl chloride In toluene at 90℃; Stage #2: methylamine hydrochloride With N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 0.25h; Inert atmosphere; 49A Example 49A 3-(Chloromethyl)-N-methylbenzenecarboxamide 5 g (29.31 mmol) of 3-chloromethylbenzoic acid were suspended in 20 ml of abs. toluene, 5.23 g (43.96 mmol) of thionyl chloride were added dropwise and the mixture was stirred at 90° C. overnight. After cooling to RT, excess thionyl chloride and toluene were evaporated and the residue was dried under high vacuum for 1 h. Under argon, the residue was dissolved in 40 ml of abs. dichloromethane and cooled to 0° C., and 2.18 g (32.24 mmol) of methylamine hydrochloride were added. At 0° C., 7.58 g (58.62 mmol) of N,N-diisopropylethylamine were slowly added dropwise, and the reaction mixture was stirred at 0° C. for 15 min. 100 ml of dichloromethane were added, and the reaction mixture was washed three times with water and once with saturated aqueous sodium chloride solution. The organic phase was dried over sodium sulfate, filtered and concentrated using a rotary evaporator. Yield: 5.28 (98% of theory) LC-MS (Method 6): Rt=0.75 min; MS (ESIpos): m/z=184 [M+H]+. 1H NMR (400 MHz, DMSO-d6): δ=8.53-8.45 (m, 1H), 7.91 (s, 1H), 7.79 (d, 1H), 7.58 (d, 1H), 7.47 (t, 1H), 4.81 (s, 2H), 2.78 (d, 3H).
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