Structure of 149968-11-6
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CAS No. : | 149968-11-6 |
Formula : | C28H22ClNO3 |
M.W : | 455.93 |
SMILES Code : | O=C(C1=CC=CC=C1CCC(C2=CC=CC(/C=C/C3=NC4=CC(Cl)=CC=C4C=C3)=C2)=O)OC |
MDL No. : | MFCD08063844 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P280-P305+P351+P338 |
* 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 |
---|---|---|
85 - 86% | With tetrabutylammomium bromide; triethylamine;palladium diacetate; In toluene; at 80℃; for 6h;Product distribution / selectivity; | Example 1; 100 gm of l-(3-(2-(7-chloro-2-quinolinyl)ethenylphenyl)-2-propen-l-ol and 93.4 gm of methyl-2-iodobenzoate are suspended in 100 ml toluene. To this 25 gm of tetrabutylammonium bromide is added followed by 41.2 gm of triethylamine and 0.5 gm of Palladium acetate. The reaction mass is heated to 800C for 6 hrs. The reaction mass is cooled and extracted with toluene (1200 ml) and the residue is again extracted with 500 ml x 2 of toluene. The toluene layer is concentrated and the residue after crystallization is filtered, washed and dried at 550C under vacuum to get 120 gm of methyl-2-(3-(2-(7-chloro-2- quinolinyl)-ethenyl)phenyl)-3-oxopropyl)benzoate. Water content (by Karl Fisher) = 0.15%; Chemical assay (by HPLC) = 98.5%; Yield = 85% (by theory).; Example 2 (Recycling procedure); 100 gm of l-(3-(2-(7-chloro-2-quinolinyl)ethenylphenyl)-2-propen-l-ol and 93.4 gm of methyl-2-iodobenzoate are suspended in the above residue. To this 41.2 gm of triethylamine is added. The reaction mass is heated to 800C for 6 hrs. The reaction mass is cooled and extracted with toluene (1200 ml) and the residue is again extracted with 500 ml x 2 of toluene. The toluene layer is concentrated and the residue after crystallization is filtered, washed and dried at 55C under vacuum to get 121 gm of methyl-2-(3-(2-(7-chloro-2- quinolinyl)-ethenyl)phenyl)-3-oxopropyl)benzoate. Water content (by Karl Fisher) = 0.13%; Chemical assay (by HPLC) = 98.6%; Yield = 86% (by theory)The above example can be repeated up to a maximum of 5 batches without affecting the yield and quality parameters. |
83% | With Methyltriphenylphosphonium bromide; triethylamine;palladium diacetate; In toluene; at 80℃; for 22h;Product distribution / selectivity; | Example 4; 100 gm of l-(3-(2-(7-chloro-2-quinolinyl)ethenylphenyl)-2-propen-l-ol and 93.4 gm of methyl-2-iodobenzoate are suspended in 100 ml toluene. To this 35 gm of methyl triphenyl phosphonium bromide is added followed by 41.2 gm of triethylamine and 0.5 gm ofPalladium acetate. The reaction mass is heated to 800C for 22 hrs. The reaction mass is cooled and extracted with toluene (1200 ml) and the residue is again extracted with 500 ml x2 of toluene. The toluene layer is concentrated and the residue after crystallization is filtered, washed and dried at 550C under vacuum to get 117 gm of methyl-2-(3-(2-(7-chloro-2- quinolinyl)-ethenyl)phenyl)-3-oxopropyl)benzoate. Water content (by Karl Fisher) = 0.19%;Chemical assay (by HPLC) = 98.24%; Yield = 83% (by theory) |
81.5% | With tetraphenylphosphonium bromide; triethylamine;palladium diacetate; In toluene; at 80℃; for 22h;Product distribution / selectivity; | Example 3; 100 gm of l-(3-(2-(7-chloro-2-quinolinyl)ethenylphenyl)-2-propen-l-ol and 93.4 gm of methyl-2-iodobenzoate are suspended in 100 ml toluene. To this 35 gm of tetraphenyl phosphonium bromide is added followed by 41.2 gm of triethylamine and 0.5 gm of EPO <DP n="7"/>Palladium acetate. The reaction mass is heated to 8O0C for 22 hrs. The reaction mass is cooled and extracted with toluene (1200 ml) and the residue is again extracted with 500 ml x 2 of toluene. The toluene layer is concentrated and the residue after crystallization is filtered, washed and dried at 550C under vacuum to get 115 gm of methyl-2-(3-(2-(7-chloro-2- quinolinyl)-ethenyl)phenyl)-3-oxopropyl)benzoate. Water content (by Karl Fisher) = 0.14%; Chemical assay (by HPLC) = 98.1%; Yield = 81.5% (by theory) |
With triethylamine;palladium diacetate; In tetrahydrofuran; toluene; for 24h;Heating / reflux;Product distribution / selectivity; | EXAMPLE 11 : PREPARATION OF 2-(3-(3-[2-(7-CHLORO-QUINOLIN^-YL)-VINYL]- PHENYL}-3-OXO-PROPYL)-BENZOIC ACID METHYL ESTER OF FORMULA XII:Toluene (500 ml), 3-[2-(7-chloro-quinolin-2-yl)-vinyl] benzaldehyde (50 g) were taken into a round bottom flask and stirred for about 10 minutes. The reaction mass was then cooled to 0 to -10 0C. Then Vinyl Magnesium bromide (1 M solution in THF) (230 ml) was added slowly at about 0 to -100C under nitrogen atmosphere. After the addition was complete, the reaction mass was maintained at 0 to -100C for about 2 hours. After the reaction was completed, the reaction mass was quenched with 10 % aqueous acetic acid solution (300 ml) below 10 0C . Toluene (250 ml) was then added to the reaction mass, and the temperature of the reaction mass was raised to 25-35 0C and stirred for about 30-45 minutes. The organic layer was separated and the aqueous layer was extracted with toluene (150 ml). The combined organic layer was washed with 5 % aqueous sodium bicarbonate solution (250 ml) followed by washing with water (2X400 ml). The organic layer was distilled azeotropically to remove the traces of water until the reaction volume was 400 ml and then cooled to 25-35 0C. Methyl 2-iodo benzoate (22.4 ml), THF (25 ml) and triethylamine (65.1 ml) was added to the residual organic layer. Palladium acetate (0.25 g) was added and the reaction mass was heated to reflux and maintained under reflux for about 24 hrs. After the reaction was completed, EPO <DP n="33"/>the reaction mass was filtered under hot condition and washed the filtered bed with toluene (100 ml). The combined filtrate was washed with water (2 X250 ml) under hot condition (60-70 0C). The toluene layer was Distill off completely under vacuum below 600C. Then toluene (75 ml) was added to the reaction mass and heated to 70-80 0C to get the clear dissolution. The solution was then cooled to about 25-35 0C and maintained for about 2 hours. Then the reaction mass was further cooled to 0-5 0C and stirred for about 4 hours. The separated solid was filtered and washed with chilled toluene (25 ml) and finally washed with hexanes (100 ml). The wet compound was dried at 50-550C under vacuum to afford 45 g of the title compound. | |
With triethylamine;palladium diacetate; In acetonitrile; for 6h;Heating / reflux; | Example 2: Synthesis of methyl 2-[3-[(E)-3-(2-(7-chloro-2-quinolinyl)ethenyl)phenyl]-3-oxopropyl]benzoate; The crude slurry of example 1 in acetonitrile was treated with methyl 2-iodobenzoate (44.6 g, 0.17 mol), triethylamine (35.6 mL, 0.254 mol) and palladium acetate (0.36 g, 1.7 mmol). The mixture was degassed and heated at reflux under nitrogen for 6 hours. Then, the hot solution was filtered through cellulose (Solka Floc) to remove any precipitated palladium. When the filtrate cooled to ambient temperature, the desired title product crystallized from solution. After one hour at ambient temperature, the suspension was filtered. The filter cake was washed consecutively with 130 mL acetonitrile, 100 mL acetonitrile/water (1:1), 100 mL water and finally 150 mL acetonitrile. After drying, the title product was obtained as a pale-yellow solid (53 g, 69% referring to the benzaldehyde of Example 1). 1H NMR complies with EP 0 480 717 B (example 16, step 3). | |
With triethylamine;palladium diacetate; In toluene; at 100℃;Reflux; | In a 2 ltr 4-necked flask equipped with a thermometer and mechanical stirrer, methyl 2- iodobenzoate( 105.6 g, 0.40 moles), triethyl amine (78 g, 0.77 moles) and palladium acetate(0.48 g, 0.007 moles) was added in a solution of [E]-l-[3-[2-(7- chloro-2-quinolinyl)- ethenyl]-phenyl]-2-propen-l-ol in toluene (obtained from example 2). Reflux the reaction mass for 24 to 30 hrs at 100 0C (+/-5 0C). Filter the salt/catalyst and filtrate washed with water and 10%sodium chloride solution. Recover the solvent under vacuum and product was crystallized in methanol, toluene, acetonitrile or mixture thereof. Filter the product and wash with methanol, toluene, acetonitrile or mixture thereof. Dry the material 40- 45 0C for 4 - 6 hrs to obtain pure Methyl-[E]-2-[3-[3-[2-(7- chloro-2-quinolinyl)-ethenyl]-phenyl] -3-oxo- propyl]-benzoate ( 1 10 g, HPLC purity 99%) | |
With triethylamine;palladium diacetate; In acetonitrile; at 80 - 85℃; for 12 - 15h; | EXAMPLE 10: Preparation of MethyI-[E]-2-[3-[3-[2-(7-Chloro-2-quinolinyI) ethenyl] phenyI]-3-oxopropyl]benzoate (VI) To a 1.01t/4 neck round bottom flask fitted with a mechanical stirrer, thermometer pocket and calcium chloride drying tube under nitrogen gas atmosphere, were successively charged crude 1-[3-[2-(7-Chloro-2-quinolinyl)ethenyl]phenyl]-2-propen-l-ol (II) (125 g, 92.5 % pure), acetonitrile, methyl-2-iodobenzoate (100 g, 0.38 mol) and triethylamine (112 mL ) and the mixture was stirred for 15 min. Palladium acetate (1.0 g) wasthen added and the mixture was slowly heated to reflux at 80 to 85 C and progress of the reaction was monitored by TLC. After the reaction was(12-15 hr), fresh acetonitrile was added to the reaction mixture and the hot solution was filtered through hyflow bed to remove the palladium salts and then allowed to stir at 20 to 25 C for 8 hr by which time most of the product had precipitated out. The solid was filtered and successively washed with cold (5 to 10 C) acetonitrile (125 mL), mixture of water and acetonitrile (125 mL +125 mL each), slurry washed with cold acetonitrile (125 mL) and finally with hexanes ( 125 mL) and dried at 55 to 60 C to afford crude keto ester (VI) as a brownish colored powder. Yield = 111.2 g ( 69.6% on 100 % basis); Purity (HPLC ) =97.21%; Assay (HPLC ) = 94.34 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With lithium chloride;palladium diacetate; In hexane; ethyl acetate; N,N-dimethyl-formamide; toluene; | Step 2 Methyl 2-(3-(3-(2-(7-chloro-2-quinolinyl)ethenyl)phenyl)-3-oxopropyl)benzoate A degassed suspension of the product of Step 1 (50.3 g, 156 mmol), n-Bu4 NCl (86.0 g, 312 mmol), LiOAc.2H2 O (41.2 g, 390 mmol), LiCl (6.84 g, 156 mmol), Pd(OAc)2 (1.00 g, 4.7 mmol), and methyl 2-iodobenzoate (41.00 g, 156 mmol) in DMF (300 mL) was stirred for 3 hours at 90 C. The dark red solution was then cooled to r.t. and poured into 2 L of ice cold H2 O. The product was extracted with hot EtOAc, dried over Na2 SO4, filtered and concentrated to dryness. It was dissolved in 600 ml of hot toluene and filtered through a small silica pad (1 L). The title product was finally recrystallized from EtOAc:hexane 1:1 (1.2 L). The title product was finally recrystallized from EtOAc:hexane 1:1 (1.2 L). Recrystallization of the mother liquors in EtOAc:hexane 1:3 (400 mL) afforded a second crop of the title compound. 1 H NMR (CDCl3): delta3.40 (4H, s), 3.92 (3H, s), 7.25-7.52 (6H, m), 7.63 (1H, d), 7.70-7.82 (3H, m), 7.95 (2H, d) 8.05 (1H, br s), 8.11 (1H, d), 8.29 (1H, br s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With palladium-cobalt nanocapsules with 10percent graphene; In N,N-dimethyl-formamide; at 95℃; for 10h;Inert atmosphere; | A dry 100 mL three-necked round bottom flask was charged with 300 mg of prop-2-en-1-ol (300 mg)200 mg o-bromobenzoate,20mg palladium-cobalt nanocapsules containing 10% by mass of graphene,Nitrogen gas was added 20 ml of anhydrous N, N-dimethylformamide,Then 1.7 mL of diisopropylamine was added dropwise,95 oC for 10 hours,After the complete reaction of the starting material (E) -1- (3- (2- (3- (2- (7-chloroquinolin-2-yl) vinyl) phenyl) prop- 2-en-1-ol was monitored, the reaction was stopped and the reaction was allowed to cool to room temperature.To control the reaction system anhydrous oxygen-free environment. |
Tags: 149968-11-6 synthesis path| 149968-11-6 SDS| 149968-11-6 COA| 149968-11-6 purity| 149968-11-6 application| 149968-11-6 NMR| 149968-11-6 COA| 149968-11-6 structure
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