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CAS No. : | 1031-15-8 | MDL No. : | MFCD00797851 |
Formula : | C19H18ClP | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | QRPRIOOKPZSVFN-UHFFFAOYSA-M |
M.W : | 312.77 | Pubchem ID : | 9879809 |
Synonyms : |
|
Signal Word: | Danger | Class: | 9 |
Precautionary Statements: | P501-P273-P270-P264-P280-P391-P332+P313-P362-P301+P312+P330-P302+P352+P312-P305+P351+P338+P310 | UN#: | 3077 |
Hazard Statements: | H302+H312-H315-H318-H411 | Packing Group: | Ⅲ |
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 |
---|---|---|
With sodium hydride In dimethyl sulfoxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at 20℃; for 0.5h; Inert atmosphere; Stage #2: cycloactanone In tetrahydrofuran; hexane at 0 - 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.4% | In benzene for 4h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With n-butyllithium In hexane; benzene at 25℃; for 4h; Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With n-butyllithium In tetrahydrofuran at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With n-butyllithium In tetrahydrofuran -20 deg C to room temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydride In tetrahydrofuran 1.) 50-60 deg C, 2.) RT, overnight; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 16% 2: 43% 3: 75% | With hydroxylamine hydrochloride In ethanol; water at 140℃; for 24h; bomb tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 76% 2: 58% | In tetrahydrofuran at -30℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 76% 2: 58% | In tetrahydrofuran at -30℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50.6% | In benzene at 50℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In tetrahydrofuran; benzene for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In acetonitrile at 20℃; for 240h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With n-butyllithium In tetrahydrofuran at -78 - 25℃; | |
55% | With n-butyllithium at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium <i>tert</i>-butylate; sodium amide In diethyl ether at -78 - 20℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With sodium tetrahydroborate In ethanol for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With sodium hydrogencarbonate In ethanol; water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50.4% | Stage #1: methyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 2h; Stage #2: (2S,4R)-N-benzyl-4-(tert-butyldimethylsilyloxy)pyrrolidine-2-carbaldehyde In tetrahydrofuran at 0 - 5℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; | |
85% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 1h; Stage #2: (+)-dihydrocitronellal In tetrahydrofuran; hexane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
180 mg | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In diethyl ether; hexane at -40℃; for 1h; Stage #2: (S)-5-{(4R,5R)-5-[(E)-(S)-2-(tert-Butyl-dimethyl-silanyloxy)-3-methyl-4-(2-methyl-thiazol-4-yl)-but-3-enyl]-2,2,4-trimethyl-[1,3]dioxolan-4-yl}-2-methyl-pentanal In diethyl ether; hexane at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With potassium <i>tert</i>-butylate In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at 25℃; for 4h; Stage #2: 1-[(nonafluorobutane)sulfonyl]-1H-benzotriazole In tetrahydrofuran; hexane at 25℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In diethyl ether at -20℃; for 0.5h; Stage #2: 2-acetyl-3a-methyloctahydroindene-2-carboxylic acid methyl ester In diethyl ether at 0℃; for 80h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 50.6 percent / benzene / 3 h / 50 °C 2: benzene / 4 h / Heating | ||
Multi-step reaction with 2 steps 1: 50.6 percent / benzene / 3 h / 50 °C 2: Ph2AsCl / benzene / 4 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; n-butyllithium In tetrahydrofuran; diethyl ether; hexane; ethyl acetate | 7.F Step F: Step F: Preparation of 2-vinyl-3-hydroxy-4,5-dihydroxy-methylpyridine hydrochloride A 2 liter flask is charged with one equivalent of methyl triphenylphosphonium chloride and 600 ml. of anhydrous diethyl ether. This solution is cooled to 0° C. and one equivalent of n-butyllithium in hexane is introduced over a thirty minute period under nitrogen. When addition is complete, the solution is aged an additional 30 minutes at 0°-5° C. Then a solution of one equivalent of 2-formyl-3-acetoxy-4,5-diacetoxymethyl pyridine in 250 ml. of anhydrous ether is added dropwise with stirring over a one hour period. The reaction mixture is then aged 16 hours at room temperature, and is then cooled to 0° C. and filtered. The filtrate is concentrated to dryness under reduced pressure and treated with a mixture of 500 ml. of 2.5 N hydrochloric acid and 300 ml. of ethyl acetate. After shaking well, the organic phase is separated and discarded. The aqueous phase is extracted with 2 more 300 ml. portions of ethyl acetate and these too are discarded. The aqueous phase is then refluxed with stirring under nitrogen for 3 hours and after cooling is poured onto excess aqueous sodium bicarbonate. The crude, solid, free base is isolated by filtration and air dried. This crude solid is taken up into 300 ml. dry tetrahydrofuran and saturated with dry hydrogen chloride at 0° C. Then 300 ml. dry diethyl ether is introduced and the desired hydrochloride crystallized. It is isolated by filtration and dried in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | In tetrahydrofuran; water | 1.S Fifth Step: Fifth Step: Synthesis of 2-(2,3-Difluoro-4-n-Propyloxybiphenyl-4'-yl)-3-(Trans-4-n-Propylcyclohexyl)Propene (6) To a solution of methyltriphenyl phosphonium chloride (43.46g, 0.122 mole) in THF (100 ml), there was dropwise added, with ice-cooling, a solution of potassium t-butoxide (13.65g, 0.122 mole) in THF (50 ml) and then they were reacted at room temperature for one hour. Thereafter, to the solution, there was dropwise added a solution of 2,3-difluoro-4-n-propyloxy-4'-(1-oxo-2-(trans-4-n-propylcyclohexyl) ethyl)biphenyl (5) (33.62g, 0.0811 mole) prepared in the 4th step in THF (100 ml) over 30 minutes with ice-cooling, and the reaction was continued at room temperature overnight. After completion of the reaction, water (150 ml) was added to the reaction solution and then the latter was extracted with toluene (500 ml). The resulting organic phase was washed with water (200 ml) and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the resulting residue was purified by silica gel column chromatography (eluent: hexane) and then recrystallization (ethanol) to give the title compound, 2-(2,3-difluoro-4-n-propyloxybiphenyl -4'-yl)-3-(trans-4-n-propylcyclohexyl)propene (6) (23.72g, 0.0575 mole; yield 71%). MS/413 (M +); Δ ε= -3.5; Δ n=0.148. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium <i>tert</i>-butylate In tetrahydrofuran at 5 - 20℃; for 21h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: methyltriphenylphosphonium chloride With potassium hexamethylsilazane In tetrahydrofuran at 20℃; for 0.5h; Stage #2: 4-(5-methoxy-2-((trimethylsilyl)ethynyl)phenyl)-2-oxobutyl acetate In tetrahydrofuran at 20℃; for 0.5h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.6% | In methanol to soln. H2PtCl6*6H2O and SnCl2*2H2O in methanol added soln. (Ph3PCH3)Cl in methanol; ppt. filtered, washed with methanol and air-dried, recrystn. by dissoln. in acetone and slow addn. methanol; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.7% | With HCl In water to soln. K2PtCl4 and SnCl2*2H2O in 3 M HCl added soln. (Ph3PCH3)Cl in 3M HCl; ppt. filtered, washed with 3 M HCl and methanol and air-dried, recrystn. from acetone/methanol; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol addn. ethyl acetate to heated soln.;; pptn. washed with ethanol-ethyl acetate mixture (1:1) and dried over H2SO4 in vacuum;; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.5% | With sodium hydride In dimethyl sulfoxide Wittig reaction;; chromatography on Al2O3 with petroleum ether;; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | In dichloromethane byproducts: ClSiMe3; exclusion of moisture, dropwise addn. of PPH3MeCl soln. to a suspn. of WCl4(NCl) at room temp., cooling to -40°C, slow dropwise addn. of CH3SeSi(CH3)3 soln., stirring for 2.5 h at room temp.; evapn., dissolving in CH2Cl2, crystn. on cooling of a saturated CH2Cl2 soln. to 4°C, elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In dichloromethane addn. of soln. of PPh3MeCl to suspn. of Ru complex, stirring, 30 min; washing ppt. with CH2Cl2, drying in vac. (further prod. isolated by concg. mother liquor); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With sodium hydride In dimethyl sulfoxide Wittig reaction;; column chromatography on Al2O3 with petroleum ether;; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In dichloromethane (moisture exclusion); addn. of P2S10 to a soln. of the phosphonium-saltin CH2Cl2, the suspn. is warmed in a 60°C water bath, HCl is bubbled through the soln. with stirring; after 40 min the soln. is cooled to 0°C, after several days the ppt. is filtd., dried in vac.;, elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | In dimethyl sulfoxide Me2SO added to 30 equiv of dry NaH, 41 equiv of malononitrile added in small portions, 1 equiv of Ru-complex in Me2SO added, heated at 95°C for 7 d, solvent removed, quenched with H2O, dissolved in H2O, 5 equiv of (Ph3PMe)Cl in H2O added dropwise; filtered, washed with water, vac. dried at 110°C; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In dichloromethane byproducts: NOCl; dropwise addn. of soln. of phosphonium salt to stirred suspn. of Os complex, 2 h; pptg. by cooling and addn. of CCl4; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In dichloromethane byproducts: P(C6H5)3CH3I3; under exclusion of moisture, PPh3MeCl was added to a suspn. of MoNCl3, soln. of PPh3MeI was added with stirring, 3 h; filtrated, washed (CH2Cl2), dried (vacuum); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | In neat (no solvent) carborane heated at 220.dewgree.C for 3 h; chromy. (silica gel, CH3CN-CH2Cl2), pptd. by P(CH3)(C6H5)3Cl; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | In neat (no solvent) carborane heated at 220.dewgree.C for 3 h; chromy. (silica gel, CH3CN-CH2Cl2), pptd. by P(CH3)(C6H5)3Cl; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | In hexane; water inert atm., a soln. of B compd. (hexane) treated with an aq. NaOH (0°C, stirring), a soln. of CH2O (H2O/methanol) added (0°C, 1 h), stirred (ambient temp., 12 h), aq. layer extd. (diethyl ether), exts. evapd. with H2O, pptd. by org.salt; ppt. filtered, washed (cold. water), recrystd. (CH2Cl2/hexane); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at 0 - 20℃; for 1h; Stage #2: 4-(2,6-dioxo-1,3-dipropyl-2,3,6,9-tetrahydro-1H-purin-8-yl)bicyclo[2.2.2]octane-1-carbaldehyde In tetrahydrofuran; hexane for 12.3333h; | 77 1,3-Dipropyl-8-(4-vinyl-bicyclo[2.2.2]oct-1-yl)-3,9-dihydro-purine-2,6-dione Example 77 1,3-Dipropyl-8-(4-vinyl-bicyclo[2.2.2]oct-1-yl)-3,9-dihydro-purine-2,6-dione To a stirred suspension of methyl triphenylphosphonium chloride (1.07 g, 3.0 mmol) in THF (20 ml) at 0° C. was added n-BuLi (1.4 M in hexane, 2.14 ml, 3.0 mmol). The resulting reddish-brown mixture was stirred at this temperature for 0.5 h and then at rt for 0.5 h. A solution of 4-(2,6-dioxo-1,3-dipropyl-2,3,6,9-tetrahydro-1H-purin-8-yl)-bicyclo[2.2.2]octane-1-carbaldehyde (372 mg, 1.0 mmol) in THF (10 ml) was added over a period of 20 minutes and the resulting mixture was stirred overnight (12 h). The reaction mixture was partitioned between saturated aqeuous NH4Cl (20 ml) and EtOAc (20 ml) and the aqueous phase was extracted with EtOAc (20 ml). The combined organic extracts were washed with saturated aqeuous NaCl (50 ml), dried (MgSO4), filtered and evaporated in vacuo to afford an oil that was purified by radial chromatography (2 mm plate) using a gradient of 0-5% MeOH in CH2Cl2 as eluent. Product-containing fractions were combined and concentrated to afford 140 mg (38%) of a white solid. MS: 371 (MH+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 2h; Inert atmosphere; Stage #2: 3,5-dichloro-2,2,2-trifluoroacetophenone In tetrahydrofuran; hexane at -78 - 65℃; for 14h; | 9 Implementation Example 9 Synthesis of 3,5-dichloro-a- (trifluoromethyl) styrene (2): Synthesis of 3,5-dichloro-a- (trifluoromethyl) styrene (2): Under a nitrogen atmosphere, n-butyllithiumsolution in hexane (3.1 mL, 4.96 mmol) in tetrahydrofuran (20 mL) was added dropwise a solution of methyltriphenylphosphonium chloride (1.424 g, 4.54 mmol) in tetrahydrofuran (50 mL) at 0 ° C. The reaction mixture was stirred for 2 hAfter a solution of compound 1 (1.0 g, 4.13 mmol) in tetrahydrofuran (20 mL) was added dropwise at -78 ° C, the reaction was allowed to proceed for 2 hours at -78 ° CWhen the temperature was raised to 65 ° C, the reaction was refluxed for 12 hours. The reaction was then quenched by adding 100 mL of saturated ammonium chloride solution to the mixture.After removing the tetrahydrofuran, the mixed solution was extracted with diethyl ether (20 mL '3). The organic phases were combined and washed with saturated brine2), dried over anhydrous magnesium sulfate, filtered, stripped of solvent and distilled to give 0.64 g of a colorless transparent liquid in 65% yield. |
With potassium methanolate In tetrahydrofuran at 18 - 50℃; for 5.25h; | S.5.3 Example S.5.3.: Synthesis of 1 ,3-dichloro-5-(1-trifluoromethyl-vinyl)-benzene(Compound example no.3 of table C.1 ); To a suspension of methyl-triphenylphosphonium chloride (9.9 g, 0.03 mol) and 3,5- dichloro-2,2,2-trifluoro acetophenone (10.0 g, purity 65%, 0.026 mol) in THF (97 ml.) was added a suspension of KOMe (2.49 g, 0.033 mol) in THF (55 ml.) at 18-200C within 15 min. After 5 h at 50°C, 76 ml. solvent was distilled off under reduced pressure 48°C, 400 mbar. N-heptane 100 ml. was added to the reaction mixture and cooled to 100C. The precipitate was filtered off and the filter cake was washed with 100 ml. of n- heptane. The filtrate was evaporated to give the title compound, (10.2 g, 71 %) as an oil (purity 45% ace. to g.c). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In water under Ar; MePPh3 added to aq. soln. of carborane salt; ppt. washed with water; vac. dried, crystd. from CH2Cl2 by carefully adding hexane onto the top; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.606 g | With potassium <i>tert</i>-butylate In tetrahydrofuran; dichloromethane at 0℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With potassium <i>tert</i>-butylate at 0 - 20℃; for 24.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: C41H68O5Si2 With sulfur trioxide pyridine complex; triethylamine In dichloromethane; dimethyl sulfoxide at 0℃; Stage #2: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h; Stage #2: (7-methoxyquinolin-4-yl)(4-nitrophenyl)methanone In tetrahydrofuran; hexane at -78 - 20℃; | 382.1 7-Methoxy-4-(1-(4-nitrophenyl)vinyl)quinoline Step 1: 7-Methoxy-4-(1-(4-nitrophenyl)vinyl)quinoline To a mixture of methyltriphenylphosphonium chloride (0.54 g, 1.7 mmol) in THF (10 mL) at -78° C. was added n-butyllithium, 2.5 M in hexanes (0.80 ml, 2.0 mmol). After 20 min, a mixture of (7-methoxyquinolin-4-yl)(4-nitrophenyl)methanone (0.177 g, 0.57 mmol) in THF (5 mL) was slowly added. After 10 min, the mixture was allowed to warm to RT. The reaction was quenched with saturated aqueous NH4Cl. The mixture was diluted with EtOAc and washed with water and brine. After drying the organic fraction with Na2SO4, the solvent was removed in vacuo and the residue purified by silica gel chromatography using 40-100% hexanes:EtOAc to afford 7-methoxy-4-(1-(4-nitrophenyl)vinyl)quinoline as a yellow foam. MS: M+H+=307.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: methyltriphenylphosphonium chloride With lithium hexamethyldisilazane In tetrahydrofuran at 20℃; for 0.5h; Stage #2: ethyl 1-(6-(3-formyl-5-methylthiophen-2-yl)pyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazole-4-carboxylate In tetrahydrofuran at 20℃; for 3h; | Intermediate 4-13. Ethyl 1-(6-(5-methyl-3-vinylthiophen-2-yl)pyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazole-4-carboxylate Intermediate 4-13. Ethyl 1-(6-(5-methyl-3-vinylthiophen-2-yl)pyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazole-4-carboxylateTo a suspension of methyltriphenylphosphonium chloride (CAS 1031 -15-8, 1 .72 g, 5.50 mmol) in THF (5 mL) at room temperature was added LHMDS (5.13 mL, 5.13 mmol). The resulting yellow suspension was stirred at room temperature for 0.5 h. To the suspension was then added a solution of Intermediate 4-11 (1 .5 g, 3.66 mmol) in THF (1 mL), and then the mixture was then stirred at room temperature for 3 h. The reaction was then quenched with sat. aq. NH4CI. The mixture was then extracted with CH2CI2. The organic layer was then dried over Na2S04, filtered and then concentrated. The resulting residue was purified by silica gel flash column chromatography (heptane/EtOAc = 1/0 to 0/1 ) to afford the title compound. MS (ESI+) m/z 408.2 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With n-butyllithium In tetrahydrofuran at 0℃; for 2h; Inert atmosphere; | 28 To a solution of methyltriphenylphosphonium chloride (2.95 g, 8.51 mmol, 4 eq.) in anhydrous THF (20 mE) was added n-l3uEi (3.2 mE, 8.1 mmol, 3.8 eq.) dropwise at -70° C. under nitrogen atmosphere. The mixture was stirred at 0° C. for 1 h. A solution of38-8 (1.2 g, 2.13 mmol) in anhydrous THF (3 mE) was added dropwise at 0° C. under nitrogen atmosphere. The solution was stirred 0° C. for 2 h. The reaction was quenched with NH4C1 and extracted with EtOAc. The organic layer was washed with brine and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (20% EtOAc in hexane) to give 38-9 (0.9 g, 75%) as a white solid. |
75% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at -70 - 0℃; Inert atmosphere; Stage #2: C30H36N2O7Si In tetrahydrofuran at 0℃; for 2h; Inert atmosphere; | 28 Example 28 Compound 38 To a solution of methyltriphenylphosphonium chloride (2.95 g, 8.51 mmol, 4 eq.) in anhydrous THF (20 mL) was added n-BuLi (3.2 mL, 8.1 mmol, 3.8 eq.) dropwise at -70° C. under nitrogen atmosphere. The mixture was stirred at 0° C. for 1 h. A solution of 38-8 (1.2 g, 2.13 mmol) in anhydrous THF (3 mL) was added dropwise at 0° C. under nitrogen atmosphere. The solution was stirred 0° C. for 2 h. The reaction was quenched with NH4Cl and extracted with EtOAc. The organic layer was washed with brine and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (20% EtOAc in hexane) to give 38-9 (0.9 g, 75%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1017 kg | In methanol at 50 - 110℃; for 8h; Autoclave; Large scale; | 1 according to the requirements triphenyl phosphonium weighed 900kg, chloride of 270kg, the molar ratio of methanol to 825kg, and triphenyl phosphonium chloride is 1: 1.5, with triphenylphosphonium methanol molar ratio of 7.5: 1;2), has in the above step 1) was weighed good methanol and triphenylphosphonium placed in a pressure capacity of 3000L reactor, reactor pressure vessel is provided on the pressure for cooling the reactor jacketed;3), open the steam inlet valve is heated to triphenylphosphonium completely dissolved in methanol, and then turn jacketed pressure reactor cooling control pressure within the reaction vessel temperature was maintained at 55 , turn off the steam inlet valve , the addition of methyl chloride, methyl chloride starts through the control pressure in the autoclave was 9kg / cm & lt2~ 10kg / cm & lt2;Methyl chloride was added when the temperature must be strictly controlled, if the temperature is too high, the pressure inside the autoclave to increase rapidly, leading to added difficulties methyl chloride, it is preferable that in the 50 ~ 60 , in this case the implementation of control at 55 .Further pressure in the pressure of the reactor but also control, if the pressure is too high, prone to accidents, the pressure is too low, is not conducive to the progress of the reaction, preferably 9kg / cm & lt2~ 10kg / cm & lt2, in this embodiment, the control vessel inner pressure of 9.5kg / cm & lt2.4) After completion of the dropwise addition of methyl chloride, the reaction temperature of the control pressure within the autoclave to a temperature of 110 deg.] C, the autoclave pressure 10kg / cm & lt2or less, and incubated 6 hours;5), was heated under reflux began, after 2 hours at reflux, to close the steam inlet valves, with pressure jacketed kettle reactor jacket cooling;6) After cooling to room temperature, the material was centrifuged, after centrifugation, the liquid material into the primary product of the mother liquor and solids;7), in the above step 6) obtained in solid primary product into the dryer drying, drying temperature of 100 ~ 105 , drying 12 hours; drying of the product after the purity test, if purity of greater than or equal to 99%, then dried and bagged products stand; if the product purity of less than 99%, then recrystallized until a purity greater than or equal to 99%, then bagging.The recrystallization process: taking a weight ratio of 2: 5 of dry product and mixed with methanol, heated to dissolve, allowed to stand for 48 hours after centrifugation, and the mother liquor to obtain a solid product, the solid product was dried and tested purity.All products weighed after bagging give triphenylmethyl phosphonium chloride products 1017kg |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.5h; Inert atmosphere; Stage #2: tert-butyl 4-oxo-1-oxa-9-azaspiro[5.5]undecane-9-carboxylate In tetrahydrofuran; hexane at 0 - 20℃; for 18h; Inert atmosphere; | 1 4.2.3. General procedure for the preparation of compounds 3h-o General procedure: n-BuLi (2.5 M in hexane, 4 mL, 10.0 mmol) was added dropwise under argon to a 0 °C suspension of the respective alkylphosphoniumchloride (10.0 mmol) in THF (50 mL). The mixture was stirred for 30 min whereupon a solution of 10 (2.42 g, 9.0 mmol) in THF (10 mL) was added. The reaction mixture was allowed to warnup to rt and stirred at that temperature for 18 h. At that point, sat. aq NH4Cl (25 mL) was added and the mixture was diluted with ethyl acetate (50 mL) and water (20 mL). Organic phase was separated and the aqueous phase was additionally extracted with ethyl acetate (2 x 50 mL). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was fractionated on silica gel using 0→5% ethyl acetate in hexanes as eluent. Fractions containing the olefination product (according to LC MS analysis) were pooled and concentrated to dryness. The material thus obtained was used in the subsequent steps without further purification.To a solution of this material in EtOH (20 mL/mmol assuming 100% purity of the product in the previous step) HCOONH4 (4 mmol/mmol) and 10% Pd on carbon (37 mg/mmol) were added and the resulting mixture was heated at reflux for 12 h. The mixture was cooled to rt and filtered through a plug of Celite (subsequently washing the latter with EtOH). The combined filtrate and washings were concentrate to dryness. The residue was partitioned between water (50 mL) and ethyl acetate (50 mL). The organic layer was separated and the aqueous layer was additionally extracted with ethyl acetate (2 x 50 mL). The combined organic extracts were washed with 3% aqueous citric acid, 5% aqueous NaHCO3 and brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. Without further purification, the residue was dissolved in CH2Cl2 (3 mL/mmol calculated assuming 100% purityof the material obtained in the previous step), the solution was cooled to 0 °C and TFA (1 mL/mmol) was added. The mixture thus obtained was stirred at 0 °C for 6 h and then concentrated to dryness to provide, after crystallization from isopropyl alcohol, the target spirocyclic piperidine as a trifluoroacetate salt. Compounds 3h, 3j, 3m-n were converted to hydrochloride salts by treatment of their rt solutions in 1,4-dioxane with 4 M HCl in 1,4-dioxane followed by stirring for 3 h, evaporation of the volatiles in vacuo and crystallization from isopropyl alcohol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | Stage #1: methyltriphenylphosphonium chloride With sodium hexamethyldisilazane In tetrahydrofuran; toluene at 0℃; for 0.75h; Inert atmosphere; Stage #2: ethyl 2-(2-( 1,3-dioxolan-2-yl)phenyl)-2-oxoacetate In tetrahydrofuran; toluene at 20℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: methyltriphenylphosphonium chloride With sodium hexamethyldisilazane In tetrahydrofuran; toluene at 0℃; for 0.75h; Inert atmosphere; Stage #2: 1-[2-(1,3-dioxolan-2-yl)phenyl]-2,2-difluoro-2-(phenylsulfonyl)-1-ethanone In tetrahydrofuran; toluene at 20℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | In tetrahydrofuran; toluene at 75℃; Inert atmosphere; Schlenk technique; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With sodium hydride In tetrahydrofuran at 40℃; for 5h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 40℃; for 6h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 40℃; for 9h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | Stage #1: methylmagnesium chloride; dichlorotriphenyl-λ4-phosphane In tetrahydrofuran; dichloromethane at 0℃; for 0.75h; Inert atmosphere; Stage #2: With hydrogenchloride In diethyl ether; water for 0.166667h; | |
98% | In tetrahydrofuran; dichloromethane at 0℃; for 1h; | Methyltriphenylphosphonium chloride, 6a To a DCM solution of 4 (0.2M in DCM, 25.00 mL, 5.00 mmol) a solution of MeMgCl (3.0M in THF, 3.35 mL, 10.05 mmol) was addedat 0 °C and the mixture was stirred at 0 °C for 1 hour afterwhich time it was quenched by HCl (2.0M in Et2O,5.00 mmol), concentrated in vacuo to yield an oily residuewhich was treated with DCM (50 mL) and aqueous NaCl(2.0 M, 2 × 10 mL). The DCM layer was washed with an equal volume of saturated aqueous NaCl. The organic layerwas eluted through sodium sulfate (10 g) and concentratedin vacuo to yield a clear oily residue, which crystallized onstanding. Recrystallization from chloroform/ethyl acetateafforded 6a (1.53 g, 98%) as fine white crystals: MP 219-221 °C, HRMS (ES+) m/z: calculated for C19H18P+277.1146, found 277.1135 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.5h; | 302.D 1,1-difluoro4-methylenecyclohexane (0927) Butyllithium (12.32 ml, 2.5 M solution in hexanes) was added to a solution of methyltriphenylphosphonium chloride (9.63 g) in tetrahydrofuran (50 ml) at 0° C., and the reaction was stirred for 5 minutes. 4,4-Difluorocycleohexanone (3.76 g) in dioxane (150 ml) was then added, and the reaction was stirred for 30 minutes. Water (3 ml) was added, and then hexane (150 ml) was slowly added, the reaction was filtered, and the solution carried on. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | Stage #1: methyltriphenylphosphonium chloride; Boc-tropinone With n-butyllithium In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #2: Boc-tropinone In tetrahydrofuran at 0 - 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at -78 - 20℃; for 0.5h; Inert atmosphere; Stage #2: 17-((tert-butyldimethylsilyl)oxy)-10,13-dimethylhexadecahydro-3H-cyclopenta[a]phenanthren-3-one In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: methyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #2: (E)-5-methyl-7-((1-(pyrimidin-2-yl)-1H-indol-2-yl)methylene)cycloheptane-1,4-dione In tetrahydrofuran for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With ammonium chloride at 110℃; for 12h; Sealed tube; | General procedure for the synthesis of phosphonium salts 3 General procedure: As shown in Tables 1 and 2, phosphine, acid and orthoformate in a mol ratio of 1:1:5 were added to the reaction tube. The reaction mixture was stirred at 110 °C. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the excessed orthoformate was evaporated under reduced pressure. The obtained residue was recrystallized with dichloromethane andethyl acetate, and washed with ethyl acetate and petroleum ether .The product was dried in a vacuum oven at 60 °C overnight to obtain desired pure phosphonium salts. Methyltriphenylphosphonium chloride (3a)Yield: 51%; light brown solid; 145-147 °C; 1H NMR (500 MHz, CDCl3) d 7.83-7.69 (m, 15H), 3.27 (d, J 13.2 Hz, 3H); 13C NMR(125 MHz, CDCl3) d 135.08, 135.06, 133.16, 133.08, 130.42, 130.32,119.41,118.71,10.42, 9.97; 31P NMR (202 MHz, CDCl3) d 21.82; HRMS(ESI-MS): Calcd. for C19H18P: 277.1141, Found: 277.1143. |
51% | With ammonium chloride at 110℃; for 12h; | 16 Example 16This embodiment is a method for synthesizing a quaternary phosphonium salt flame retardant. The specific steps are as follows: Add triphenylphosphine (0.0035mol) to the two-necked flask in sequence,Ammonium chloride (0.00355mol) and trimethyl orthoformate (1.5ml) were added to the stirring bar. Heat and reflux at 110°C for 12 hours. After the reaction was completed, it was cooled to room temperature, the solvent was evaporated under reduced pressure, and recrystallized using dichloromethane, ethyl acetate, and petroleum ether. The obtained solid was washed with ethyl acetate and petroleum ether, and the white solid obtained after suction filtration was transferred to Dry overnight in a 60°C vacuum oven to obtain a solid quaternary phosphonium salt flame retardant (PFR-16), whose structural formula is: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: methyltriphenylphosphonium chloride With n-butyllithium In hexane; toluene at -78 - 20℃; Inert atmosphere; Schlenk technique; Stage #2: chloro-diphenylphosphine In hexane; toluene at 20℃; for 4.5h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: (Z)-methyl 2-(bromomethyl)-3-phenylacrylate; potassium N-methylsulfonyldithiocarbimate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: potassium N-ethanesulfonyldithiocarbamate; (Z)-methyl 2-(bromomethyl)-3-phenylacrylate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: potassium N-butylsulfonyldithiocarbimate; (Z)-methyl 2-(bromomethyl)-3-phenylacrylate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Stage #1: potassium N-octylsulfonyldithiocarbimate; (Z)-methyl 2-(bromomethyl)-3-phenylacrylate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: methyl (Z)-2-(bromomethyl)-3-(4-nitrophenyl)prop-2-enoate; potassium N-methylsulfonyldithiocarbimate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: potassium N-ethanesulfonyldithiocarbamate; methyl (Z)-2-(bromomethyl)-3-(4-nitrophenyl)prop-2-enoate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: potassium N-butylsulfonyldithiocarbimate; methyl (Z)-2-(bromomethyl)-3-(4-nitrophenyl)prop-2-enoate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: potassium N-octylsulfonyldithiocarbimate; methyl (Z)-2-(bromomethyl)-3-(4-nitrophenyl)prop-2-enoate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: (Z)-methyl 2-(bromomethyl)-3-(4-(trifluoromethyl)phenyl)acrylate; potassium N-methylsulfonyldithiocarbimate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: (Z)-methyl 2-(bromomethyl)-3-(4-(trifluoromethyl)phenyl)acrylate; potassium N-ethanesulfonyldithiocarbamate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: (Z)-methyl 2-(bromomethyl)-3-(4-(trifluoromethyl)phenyl)acrylate; potassium N-butylsulfonyldithiocarbimate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Stage #1: (Z)-methyl 2-(bromomethyl)-3-(4-(trifluoromethyl)phenyl)acrylate; potassium N-octylsulfonyldithiocarbimate In water; acetone at 20℃; for 0.25h; Stage #2: methyltriphenylphosphonium chloride In water for 0.0833333h; | Syntheses of the allyldithiocarbimates (1a-d, 2a-d and 3a-d) General procedure: A solution of 1 mmol of each allylic bromide in acetone(2 mL) was added dropwise to a stirring acetone:water(1:1 by volume) solution (10 mL) containing 1.2 mmol ofthe appropriate potassium N-R-sulfonyldithiocarbimate(Scheme 3). The mixture was stirred for up to 15 min(monitored by TLC) at room temperature. Then, water For the syntheses of compounds 1a-c, 2a-c and 3a-c, theorganic phase was concentrated under reduced pressure andthe residue was dissolved in water. Tetraphenylphosphoniumchloride (1 mmol) was added and the mixture was stirred for5 min. The yellow solid thus formed was filtered, washedwith distilled water and dried under reduced pressure forone day. As compounds 1d, 2d and 3d are oils, in thesecases tetraphenylphosphonium chloride (1 mmol) wasadded directly to the organic phase (ethyl acetate). Themixture was stirred for 5 min. Then the organic solutionwas washed with water (2 × 20 mL), the organic solventwas evaporated, and the residue was dried under reducedpressure for one day |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile; N-ethyl-N,N-diisopropylamine In acetonitrile at 20℃; for 48h; Inert atmosphere; Sealed tube; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With potassium hydrogencarbonate In toluene at 110℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | Stage #1: methyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran at 15℃; for 0.5h; Stage #2: 1-[4-(2-[tert-butyl(dimethyl)silyl]oxy}propan-2-yl)-5-fluoro-6-(4-fluorophenyl)pyridin-2-yl]-2,2-difluoroethan-1-one In tetrahydrofuran at 15℃; for 16h; Stage #3: methyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran at 15℃; for 18h; | 4-f2-( iterf-Butyl('dimethyl)silvnoxylpropan-2-yl)-6-(3,3-difluoroprop-l-en-2-yl)-3-fluoro-2-(4- fluorophenvQpvridine 163 To a solution of methyltriphenylphosphonium chloride (1.91 g, 6.12 mmol) in THF (100 mL) was added f-BuOK (686 mg, 6.12 mmol). The mixture was stirred at 15°C for 30 min. A solution of 162 (2.25 g, 5.10 mmol) in THF (25 mL) was added dropwise, and the reaction mixture was stirred at 15°C for 16 h. Additional amount of r-BuOK (686 mg, 6.12 mmol) and methyltriphenylphosphonium chloride (1.91 g, 6.12 mmol) were added at 15°C and the reaction25 mixture was stirred for another 18 h. The reaction mixture was diluted with water (100 mL) and extracted with EtOAc (2 x 300 mL). The combined organic extracts were washed with brine (100 mL) and dried (MgSO/t). The solids were removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by silica column chromatography (CH2CI2) to afford 163 (1.2 g, 54%) as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In N,N-dimethyl-formamide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | Stage #1: triphenylmethylphosphonium chloride With n-butyllithium In dichloromethane at 0 - 20℃; for 7h; Inert atmosphere; Stage #2: C16H11F3N6O In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere; | 3 In a nitrogen atmosphere, 0.175 mol of methyltriphenylphosphonium chloride and 0.705 L of dichloromethane were mixed, and stirred uniformly at 0 °C for 4 h.0.18mol of butyllithium was added to the mixed system, activated at 20°C for 7h and then cooled to 0°C, then 0.1mol of intermediate 3 and 0.235L of dichloromethane were mixed and added to the system, reacted at 20°C for 3h.Using TLC detection, the volume ratio of ethyl acetate and petroleum ether was 1:5. After the ylide reaction was completed, saturated aqueous sodium bicarbonate solution was added to quench the reaction,The solvent was evaporated under reduced pressure, extracted with ethyl acetate, and the organic phase was washed with water and saturated brine, and dried.The solvent was distilled off under reduced pressure, the concentrate was recrystallized using ethyl acetate-petroleum ether system, suction filtered, washed,The filter cake was dried in a forced air oven to obtain a light yellow solid, which was Intermediate 4, with a yield of 69% and a purity of 99.1%. |
Tags: 1031-15-8 synthesis path| 1031-15-8 SDS| 1031-15-8 COA| 1031-15-8 purity| 1031-15-8 application| 1031-15-8 NMR| 1031-15-8 COA| 1031-15-8 structure
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
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P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
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P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
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P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
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P243 | Take precautionary measures against static discharge. |
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P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
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P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
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P321 | |
P322 | |
P330 | Rinse mouth. |
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P337 | If eye irritation persists: |
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P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
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P352 | Wash with plenty of soap and water. |
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P363 | Wash contaminated clothing before reuse. |
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P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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