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[ CAS No. 93-52-7 ] {[proInfo.proName]}

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Chemical Structure| 93-52-7
Chemical Structure| 93-52-7
Structure of 93-52-7 * Storage: {[proInfo.prStorage]}
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Product Details of [ 93-52-7 ]

CAS No. :93-52-7 MDL No. :MFCD00000138
Formula : C8H8Br2 Boiling Point : -
Linear Structure Formula :- InChI Key :SHKKTLSDGJRCTR-UHFFFAOYSA-N
M.W : 263.96 Pubchem ID :7145
Synonyms :

Calculated chemistry of [ 93-52-7 ]

Physicochemical Properties

Num. heavy atoms : 10
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.25
Num. rotatable bonds : 2
Num. H-bond acceptors : 0.0
Num. H-bond donors : 0.0
Molar Refractivity : 51.96
TPSA : 0.0 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : Yes
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.59 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.39
Log Po/w (XLOGP3) : 3.27
Log Po/w (WLOGP) : 3.19
Log Po/w (MLOGP) : 3.85
Log Po/w (SILICOS-IT) : 3.53
Consensus Log Po/w : 3.25

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -3.85
Solubility : 0.0374 mg/ml ; 0.000142 mol/l
Class : Soluble
Log S (Ali) : -2.94
Solubility : 0.3 mg/ml ; 0.00114 mol/l
Class : Soluble
Log S (SILICOS-IT) : -4.56
Solubility : 0.00732 mg/ml ; 0.0000277 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 0.0
Synthetic accessibility : 2.28

Safety of [ 93-52-7 ]

Signal Word:Danger Class:8
Precautionary Statements:P280-P305+P351+P338-P310 UN#:3261
Hazard Statements:H314 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 93-52-7 ]

* 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 [ 93-52-7 ]

[ 93-52-7 ] Synthesis Path-Downstream   1~84

  • 1
  • [ 100-42-5 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
100% With selenium(IV) oxide; hydrogen bromide In diethyl ether Ambient temperature;
100% With bromine In chloroform-d1 at 20℃; for 0.5h;
99% With tetra-N-butylammonium tribromide In chloroform for 0.0333333h; Ambient temperature; ultrasonic irradiation;
99% With phenyl acetyl(2,6-dimethylphenyl)tellurocarbamate; dihydrogen peroxide; glacial acetic acid; lithium bromide In 1,4-dioxane at 20℃; for 1h;
99% With bromine In chloroform at 0 - 20℃; for 1h; Inert atmosphere; 2.2. General Procedure B: Bromination of styrene derivatives General procedure: For example the preparation of 1-(1,2-dibromoethyl)-4-methylbenzene (S5)-Bromine (260 μL, 5.07 mmol, 1.2 equiv) was added dropwise to a stirred solution of 4-methylstyrene (500 mg, 4.23 mmol, 1 equiv) in CHCl3 (8.5 mL, 0.5 M) at 0 °C under N2 atmosphere. After 5 min the reaction mixture was allowed to warm to room temperature and was stirred for 1 h. After the reaction was complete, the reaction mixture was quenched with saturated aqueous Na2S2O3 (15 mL) and diluted in CH2Cl2 (20 mL). The organic phase wasthen separated, washed with H2O (20 mL) and brine (20 mL), dried over Na2SO4, filtered,and concentrated under reduced pressure, to afford the desired product as a white solid (1.2 g,yield quant.).
99% With bromine In Carbon tetrachloride at 15 - 20℃; for 2h;
98% With sodium (meta)periodate; glacial acetic acid; lithium bromide at 25℃;
98% With N-butyl-N-methylpyrrolidinium tribromide chemoselective reaction;
98% With bromine In dichloromethane at 0℃; Inert atmosphere;
98% With sulfuric acid; sodium bromide In chloroform; lithium hydroxide monohydrate at 30℃; Electrochemical reaction; Green chemistry; regioselective reaction; Procedure for synthesis of 1,2-dibromo-1-phenylethane A solution of styrene (1.04 g, 10 mmol) in 25 ml CHCl3 was taken in a beaker-type glass-jacketed undivided cell (100 ml capacity) equipped with magnetic stirrer. To this solution, 30 ml of 25% NaBr solution (w/v) containing 2.45 g H2SO4 (25 mmol) was added. Two platinum foilel ectrodesofactive area 7.5 cm2 (3 cm x 2.5 cm) were placed carefully in the upper aqueous phase without touching the organic phase (Fig. 4). The inter electrode distance was maintained at 1 cm. The electrolysis was conducted galvanostatically at a current density of 40 mA/cm2 and the charge corresponding to 2 Faraday was passed. The organic phase was stirred with a magnetic stirrer at a rate of 40 rpm in such a way that the organic phase does not touch the electrodes. During the course of the reaction the cell voltage was measured to be 1.1-1.3 V. The electrolysis was continued until the reaction proceeded to completion. The progress of the reaction was monitored by high-performance liquid chromatography (HPLC, Shimadzu) using a Shimpack ODS-18 column (250 x 5 mm) as the stationary phase. The eluent consisted of 70:30 methanol/water. A flow rate of 1 ml per minute was employed. The samples were analyzed using an ultraviolet (UV) detector at a wavelength of 254 nm. After the completion of electrolysis, the lower organic phase was carefully separated from the reaction mixture. The aqueous portion was saved for reuse after extraction with CHCl3 (225 ml). The combined organic phase was washed with water, dried over anhydrous sodium sulfate, and distilled the solvent to get the product. Product analytical data: 1,2-dibromo1-phenylethane Mp: 71-73 °C; 1H NMR (CDCl3, 400 MHz) 7.44-7.32 (m, 3H) 5.15 (dd, J=10.6, 5.4 Hz, 1H), 4.11-3.99 (m, 1H); 13C NMR (CDCl3, 100 MHz) δ 138.2, 129.2, 128.9, 127.4, 50.9, 35.0.
97% With bromine In hexane at 20℃; for 48h;
97% With [bis(acetoxy)iodo]benzene; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 20℃; for 0.25h;
97% With allyltriphenylphosphonium bromide-bromine (1:1) In methanol for 10h; Reflux;
97% With potassium peroxomonosulfate; ammonium bromide In lithium hydroxide monohydrate; acetonitrile for 7h; Reflux; General procedure for the synthesis of dibromides: General procedure: To a solution of olefin (2 mmol) in CH3CN (10 mL) were added NH4Br (4.4 mmol) and Oxone (2.2 mmol) and the mixture was stirred at reflux temperature for the time shown in Table 2. After completion (as indicated by TLC), the reaction mixture was filtered and the solvent evaporated under reduced pressure. The products were purified by column chromatography (Hexane/EtOAc, 98:2) over silica gel.
97% With Oxalyl bromide; dimethyl sulfoxide In dichloromethane at -10 - 20℃; for 0.5h; Inert atmosphere; Bromination of Alkenes, Alkynes and Ketones; General Procedure General procedure: To a solution of (COBr)2 (0.43 mL, 3.0 mmol, 1.5 equiv) in CH2Cl2 (10mL) at -10 °C was added dropwise a solution of DMSO (0.21 mL, 3.0mmol, 1.5 equiv) in CH2Cl2 (10 mL) under an atmosphere of nitrogen. After 10 min, a solution of alkene, alkyne or ketone (2 mmol, 1.0 equiv) in CH2Cl2 (5 mL) was added. The mixture was then allowed to warm to 20-40 °C and stirred for 0.5-3 h. Distilled H2O (20 mL) was added dropwise at 0 °C. After stirring for 10 min, the organic layer was separated and washed with brine (2 × 20 mL), dried (Na2SO4), filtered and concentrated under vacuum to afford the brominated product. Most products can be obtained in high purity without further purification, except 3n, 7d, and 7f. The three products need purification by flash chromatography (silica gel, PE/EtOAc = 10:1 for 3n, PE/EtOAc= 60:1 for 7d, PE/EtOAc = 20:1 for 7f).
97% With bromine In dichloromethane at 0 - 20℃; for 1h;
97% With bromine In dichloromethane at 0 - 20℃; for 1h;
96% With bromo-dimethylsulfonium bromide In acetonitrile at 20℃; for 0.25h;
96% With urea hydrogen peroxide addition compound; trifluoroacetic acid; lithium bromide In acetonitrile at 80℃; for 1h;
96% With hydrogenchloride; NaBrO3; sodium bromide In dichloromethane; lithium hydroxide monohydrate at 20 - 45℃; 1 5.21 grams of styrene,8.58 grams of sodium bromide and 2.51 grams of sodium bromate were added to 125 milliliters of dichloromethane; a mixed solution was obtained, and 125 milliliters of 1 mol/L hydrochloric acid solution was slowly added dropwise to the mixed solution at room temperature, and the temperature was controlled below 45 ° C ; After the dropwise addition, the reaction was stirred at room temperature until the brown color of the solution disappeared; then, 0.5 g of sodium sulfite was added, the lower organic phase was layered, and after being dried with sodium sulfate, the organic solvent was removed by rotary evaporation, and the obtained product was a white powder 12.66 gram to obtain the ortho-dibromo compound;The yield of the above-mentioned synthetic ortho-dibromo compound is calculated to be 96%
95% With sulfuric acid; dihydrogen peroxide; sodium bromide at 20℃; for 1h;
95% With propane 3-bromo-1-(triphenylphosphonium) tribromide In dichloromethane at 20℃; for 0.5h; 3.3. General experimental procedure for bromination of alkenes General procedure: In a typical reaction, the alkene (3 mmol) was dissolved indichloromethane (5 mL) and stirred well for 2 min. Propane 3-bromo-1-(triphenyl phosphonium) tribromide II (3 mmol) dissolvedin dichloromethane (5 mL) andwas added to alkene solutiondropwise with constant stirring at room temperature. The progressof the reaction was monitored by TLC and GC. After completion ofthe reaction and disappearance of the yellow-orange color of reagentII, the solvent evaporated and diethyl ether was added(3 5 ml). The mixture was filtered and the solvent evaporated. The crude product thus obtained and then subjected to a shortcolumn of silica gel using a mixture of n-hexane and ethyl acetate(8:2) as the eluent. All of the isolated products are known andphysical data have been reported in the literature. The mainproducts, reaction times and isolated yields are tabulated in Table 2.To confirm, the products were subjected to DSC and GC/MS andspectra were compared and validated with the NIST library (seesupporting information).
95% With NBS In dichloromethane; dimethyl sulfoxide at 20℃; for 0.0833333h; Inert atmosphere; 2. Experimental We began with the reaction of styrene (1) with NBS. Initially, 1 (1 equiv.) and NBS (2 equiv.) were allowed to stir in DMSO (3 mL) under nitrogen at room temperature. Instantaneous generation of yellow colour and its decolouration prompted us to check the reaction progress. To our delight, the formation of two products was observed through TLC. The spectroscopic analysis confirmed the formation of vicinal dibromostyrene (2) and bromohydrin 2' (Table 1). 1H NMR and 13C NMR of both the compounds were in full agreement with the literature. In order to get vicinal dibromostyrene (2) as the sole product, the reaction was carried out under various conditions.
94% With iodic acid; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 20℃; for 0.25h;
94% With bromine In Carbon tetrachloride at 20℃; for 2h;
94% With bromine In dichloromethane at 20℃; for 2h;
93% With tetra-N-butylammonium tribromide In chloroform for 0.166667h;
93% With 1,1'-(ethane-1,2-diyl)dipyridinium bistribromide at 20℃; for 0.5h;
93% With Br3(1-)*C19H17PPol(1+) In dichloromethane at 20℃; for 2h; Darkness;
93% With 1-(N,N-diethylaminoethyl)-3-methylimidazole hexafluorophosphate; bromine In lithium hydroxide monohydrate at 10 - 20℃; for 0.25h; chemoselective reaction; typical experimental procedure General procedure: in a 25 ml flask containing BIL 1a (30%) andwater (5 ml), pure alkene 3 (3.0 mmol) was added, maintaining thetemperature between 10-20 C. Then, Br2 (3.0 mmol) was added dropwise bya syringe under continuous stirring as rapidly as the color is destroyed. After allthe bromine has been added, the resulting reaction mixture was stirred for anadditional 15 min at room temperature. Solid compounds 4 were filtrated andpurified by crystallization, while the remaining BIL/water solution was readyfor reusing. Conversely, an extraction using ethyl acetate was carried out toseparate not solid dibromide derivatives 4 from the mixture. The combinedorganic extract was washed with water and dried over anhydrous sodiumsulfate, while the remaining solution (BIL/water) was ready for reusing asabove. After evaporation of ethyl acetate the crude product was purified byflash chromatography over silica gel (ethane-diethyl ether 9:1). All products4a-k are identified with their appropriate stereoconfiguration (whereverapplicable) by comparison with authentic samples.7a,19-23
93% With DITB; dimethyl sulfoxide In dichloromethane at 25℃; for 1h; Typical procedure of bromination of alkenes using DITB/DMSO General procedure: To a mixture of DITB (2, 517.0 mg, 1.10 mmol), DMSO (41.3 mg, 0.53 mmol), in CH2Cl2 (2 mL) was added 1-dodecene (4e, 253.7 mg, 1.50 mmol), and the mixture was stirred for 1 h at 25 °C. The reaction mixtures was then diluted with ether and quenched with aqueous NaHCO3, and extracted with ether (15 mL x 3). The combined organic layers were washed with water (15 mL x 1), dried over Na2SO4, filtrated, and concentrated in vacuo. The residue was purified by silica gel column chromatography (eluent: hexane) to afford 1,2-dibromododecane (5e, 468.0 mg, 95%).
92% With lead tetraacetate; anhydrous zinc bromide In chloroform at 20℃; for 0.0833333h;
92% With trihexyltetradecylphosphonium tribromide In chloroform-d1 for 3h; Darkness; Ionic liquid;
92% With poly(diallyldimethylammonium chloride) supported tribromide for 0.5h;
92.4% With bromine In Carbon tetrachloride at 15 - 20℃; for 2h;
92.4% With bromine In Carbon tetrachloride at 15 - 20℃; for 2h;
92% With cerium(III) bromide; dihydrogen peroxide In dichloromethane; lithium hydroxide monohydrate at 20℃; 10 Example 10 3a (9.61mmol, 1g) was dissolved in DCM (45ml), FeBr2(19.22mmol, 4.14g) orCeBr3(12.49mmol, 4.75g) wasadded to the mixture of the two in severalportions, and then added to the circle The H2O2aqueous solution (30wt%, 28.83mmol, 2.94ml) wasadded to the bottom flask several times, and the reaction was stirred at room temperature for 0.5-1h.After the reaction was completed, the reaction was quenched with Na2S2O3solution (0.1M, 320 ml), and extracted with dichloromethane (100 ml).The organic phase was collected, and the aqueous phase was extracted with dichloromethane (2×50 ml).The organic phases were combined and washed with water in turn, dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 4a (FeBr2: 68%; CeBr3: 92%).
91% With CAN; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 20℃; for 0.5h;
90% With potassium permanganate; hydrogen bromide In acetonitrile
90% With tetraethylammonium bromate; potassium bromide In lithium hydroxide monohydrate at 20℃; for 0.5h; Green chemistry;
90% With selenium(IV) dioxide; hydrogen bromide In diethyl ether; lithium hydroxide monohydrate at 0 - 25℃;
88% With NBS; ferric(III) bromide; sodium bromide In acetonitrile at 60℃; Inert atmosphere;
86% With hydrogen bromide In acetonitrile Electrolysis; Flow reactor;
85% With dioxane*Br2 at 20℃; for 0.166667h;
85% With glacial acetic acid; lithium bromide at 25℃; for 2h; Green chemistry; 1 Example 1 Add 2 mmol (0.208 g) of styrene, 4.0 mmol (0.347 g) of lithium bromide to a 50 mL three-necked flask, and add 12 mL of acetic acid as the solvent.Then join1.2g Zn-Al hydrotalcite ZnAl-BrO3--LDHs intercalated with bromateMagnetic stirring was carried out at 25 °C. for 2 hours and the reaction was complete by TLC. After the reaction was completed, the resulting reaction solution was centrifuged at 6500 r/min to remove zinc aluminum hydrotalcite solids.The resulting liquid was placed in a separatory funnel, dichloromethane and deionized water were added, and the organics obtained in the reaction were extracted into a methylene chloride phase. Column chromatography silica gel was added to the obtained solution, and the solvent was distilled off under reduced pressure.The remaining mixture was separated by column chromatography. A mixture of petroleum ether and ethyl acetate in a volume ratio of 15:1 was used as an eluent to collect the eluate containing the product. The eluate was evaporated to remove the solvent to obtain a pure product.The material is, the yield is 85%.
85% With NBS; dimanganese decacarbonyl In 1,2-dichloro-ethane at 110℃; for 12h; Schlenk technique;
81% With oxone; sodium bromide at 20℃; for 0.666667h; Neat (no solvent); Mechanical ball milling;
81% With bromine In acetonitrile at 5 - 20℃; for 0.5h;
80% With N-bromo-N-sodiopolystyrenesulphonamide; sulfuric acid In chloroform for 10h; Ambient temperature;
79% With bis(dimethylacetamide)hydrogen tribromide In chloroform at 0 - 5℃;
78% With sol-gel entrapped pyridinium hydrobromide perbromide In hexane at 65℃; for 8h;
78% With maghemite(γ-Fe2O3) nanoparticle supported 2,2'-bis[3-(triethoxysilyl)propyl]imidazolium substituted diethyl ether bis(tribromide) In methanol; dichloromethane for 6h; Reflux;
78% With NBS; glacial acetic acid; lithium bromide In ethyl acetate at -25℃; for 1h; Sealed tube;
76% With ethyl triphenylphosphonium tribromide In acetonitrile at 20℃; for 0.333333h;
71% With hydrogen bromide; dimethyl sulfoxide In lithium hydroxide monohydrate; ethyl acetate at 60℃; for 0.5h;
70% With amine hydrofluoride; NBS In dichloromethane; lithium hydroxide monohydrate at 25℃; for 4.5h; Darkness; Typical Procedure for the Dibromination of Olefin 1a UsingNBS and Aqueous Ammonium Fluoride General procedure: To a solution of olefin(1a; 21 mg, 0.202 mmol, 1.0 equiv) in CH2Cl2 (1.0 mL) wasadded N-bromosuccinimide (78.3 mg, 0.44 mmol, 2.2 equiv)and saturated aqueous ammonium fluoride (0.16 mL) in theabsence of light. The resulting mixture was stirred at room temperatureand the reaction was monitored by TLC. The reactionwas quenched with saturated aqueous Na2S2O3 (5 mL) andextracted with CH2Cl2 (3 × 10 mL). The combined extracts weredried over anhydrous MgSO4 and filtered. The filtrate was concentratedunder reduced pressure and the residue was purifiedby flash column chromatography to yield the dibromide 2a(37.1 mg, 70%) as a white solid: 1H NMR (400 MHz, CDCl3): δ =7.44-7.34 (m, 5 H), 5.16 (dd, J = 10.6, 5.5 Hz, 1 H), 4.09 (dd, J =10.2, 5.5 Hz, 1 H), 4.03 (t, J = 10.4 Hz, 1 H); 13C NMR (400 MHz,CDCl3): δ = 138.66, 129.25, 128.93, 127.73, 50.98, 35.15; HRMS(EI): m/z [M]+ calcd. for C8H8Br2: 263.8967; found: 263.8972.
68% With copper (II) bromide In ethanol at 25℃; for 24h; regioselective reaction;
63% With tris(2,2′-bipyridyl)ruthenium(II) chloride; carbon tetrabromide In acetonitrile at 20℃; for 120h; Irradiation; General procedure for the bromination of phenols and alkenes General procedure: To a 10 mL round bottom flask equipped with a magnetic stir bar were added phenols or alkenes (0.1 mmol), CBr4 (33 mg, 0.1 mmol), dry CH3CN (1 mL) and Ru(bpy)3Cl2 (3.8 mg, 0.005 mmol). The mixture was irradiated with blue LEDs (1 W) at room temperature open to air until the starting material disappeared completely (monitored by TLC). After the reaction was completed, the solvent was concentrated in vacuo. The residue was purified by flash column chromatography to give the final product.
62% With tetra-N-butylammonium tribromide In dichloromethane for 1h; Ambient temperature;
62% With tetrahydropyrrole; Succinimide; NBS In chloroform at 60℃; for 1.5h;
61% With hydrogen bromide; dimethyl sulfoxide In chloroform; lithium hydroxide monohydrate at 65℃; for 12h;
58% With 2,4,4,6-Tetrabromo-2,5-cyclohexadien-1-one In dichloromethane for 48h; Ambient temperature;
57% With bromine In chloroform at 20℃;
56% With NBS; lithium bromide In tetrahydrofuran at 20℃; for 0.5h;
56% With sulfuric acid; tetrabutylammonium bromide; lithium hydroxide monohydrate; oxygen In acetonitrile at 0℃; for 0.166667h; Electrochemical reaction;
49% With Oxalyl bromide; Triphenylphosphine oxide In 1,2-dichloro-ethane at 40℃; for 24h; Molecular sieve; Inert atmosphere; Schlenk technique;
40% With NBS; copper (I) iodide In dichloromethane at 25℃;
33% With monobromodicyanomethane; 2,2'-azobis(isobutyronitrile) In benzene Heating;
16% With NBS In diethyl ether at 40℃; for 3h;
With sulfur(IV) oxide; bromine
With bromine
With 1,4-dioxane; bromine
With diethyl ether; bromine im Sonnenlicht;
With chloroform; bromine
With bromine In diethyl ether
With N,N-dibromourethane In Carbon tetrachloride
With bromine In chloroform
With NBS; N,N-dimethyl-formamide
With bromine In Carbon tetrachloride
With bromine In dichloromethane
With NBS In N,N-dimethyl-formamide Ambient temperature;
With o-tetrachloroquinone; hydrogen bromide In 1,4-dioxane Ambient temperature;
(bromination);
With bromine Yield given;
With bromine In dichloromethane Yield given;
95 % Chromat. With 2-bromo-2-methylpropane; dimethyl sulfoxide at 80℃; for 3h;
With bromine In diethyl ether at -10℃; for 2h; Yield given;
With bromine In various solvent(s) for 1h; Ambient temperature;
100 % Chromat. With poly(4-methyl-5-vinylthiazolium) hydrotribromide In dichloromethane for 1.17h; Ambient temperature;
With bromine In lithium hydroxide monohydrate; acetonitrile at 25℃; concentration dependence;
With bromine In lithium hydroxide monohydrate
With bromine In lithium hydroxide monohydrate; acetonitrile at 25℃; measurement with the use of Pt ring - Pt disc rotating electrode by bromine generated with controlled current at the disc;
With bromine In methanol at 25℃; different solvent;
With poly(4-methyl-5-vinylthiazolium) hydrotribromide (P4M5VTHT) In dichloromethane for 1.17h; Ambient temperature; other unsaturated ketones and olefins, var. time;
With 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate; 1-butyl-3-methylimidazolium tribromide at 25℃;
With bromine
With bromine In dichloromethane at 0 - 5℃;
With bromine; glacial acetic acid; lithium bromide at 20℃; for 24h;
With selenium(II) bromide
With hydrogen bromide; dihydrogen peroxide In ethanol; lithium hydroxide monohydrate at 80℃; synthesis of vicinal dibromides from olefins General procedure: To a mixture of olefin (16.8 mmol) and EtOH (60 mL) at 80 °C was added concentrated (48%) HBr (7.2 mL) dropwise over a period of 30 min followed by dropwise addition of 30% H2O2 (4.8 mL). During H2O2 addition the color of the solution changed to brown (the characteristic color of bromine). Stirring was continued until the color disappeared. The mixture was allowed to cool to room temperature, and further neutralized by addition of aqueous NaHCO3 solution until pH 6.In the case of solids (Table 1, entries 1-3), the products were separated by filtration, washed thoroughly with water and dried in air. In the case of liquids (Table 1, entries 4-6), the products were separated by extraction with CH2Cl2. The organic phase was dried over Na2SO4 and evaporated under vacuum, to afford pure dibromo compounds which were used as the reactants for the synthesis of acetylenes (as detailed below).

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[99]Location in patent: body text Potapov, Vladimir A.; Musalov, Maxim V.; Amosova, Svetlana V. [Tetrahedron Letters, 2011, vol. 52, # 36, p. 4606 - 4610]
[100]Location in patent: experimental part Shenawi-Khalil, Sanaa; Sonavane, Sachin U.; Sasson, Yoel [Tetrahedron Letters, 2012, vol. 53, # 18, p. 2295 - 2297]
  • 2
  • [ 100-42-5 ]
  • [ 2425-28-7 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 92% 2: 5% With Oxone; ammonium bromide In water; acetonitrile at 20℃; for 0.0333333h; regioselective reaction; General procedure for the synthesis of bromohydrins: General procedure: To a solution of olefin (2 mmol) in CH3CN/H2O (1:1) (10 mL) were added NH4Br (2.2 mmol) and Oxone (2.2 mmol) and the mixture was stirred at room temperature for the time shown in Table 2. After completion (as indicated by TLC), the reaction mixture was filtered and the solvent evaporated under reduced pressure. The products were purified by column chromatography (Hexane/EtOAc, 90:10) over silica gel.
91% With sodium periodate; sulfuric acid; lithium bromide In water; acetonitrile at 25℃;
1: 90% 2: 2 %Spectr. With water; hydrogen bromide; oxygen; sodium nitrite In acetonitrile at 22℃; for 5h;
1: 86% 2: 5% With potassium bromate; sulfuric acid; water; potassium bromide In dimethyl sulfoxide at 70 - 80℃; for 0.5h;
1: 13% 2: 81% With Oxone; ammonium bromide In water; acetonitrile at 20℃; for 19h;
1: 80% 2: 20% With water; oxygen; lithium bromide In tetrahydrofuran at 25℃;
1: 73% 2: 8% With (2S,3S)-3-hydroxy-2-(4-methylphenylsulfonamido)butanoic acid; water; N-bromoacetamide In <i>tert</i>-butyl alcohol at 20℃; for 1h; regioselective reaction; 4.3. General procedure for the synthesis of bromohydrins with AcNHBr General procedure: NTsLT (6) (273 mg, 1 mmol) was dissolved in t-BuOH/H2O (1:1, 4 mL), then AcNHBr (19) (165 mg, 1.2 mmol) and olefin (1 mmol) were added to the solution. The mixture was stirred at room temperature. When the yellow color of the mixture faded, the reaction was complete (also monitored by TLC). Na2SO3 (50 mg) was added to the mixture, then extracted with ethyl acetate (3×10 mL) and the organic phases were washed with brine (10 mL) and dried over Na2SO4. The solvent was removed under reduced pressure and the crude residue was further purified by column chromatography to obtain the corresponding bromohydrin products.
1: 73% 2: 17% With water; hydrogen bromide In acetonitrile Electrolysis; Flow reactor;
1: 66% 2: 30 % Chromat. With water; Selectfluor; potassium bromide In acetonitrile for 0.5h;
With potassium bromide at 20℃;
With sodium molybdate; dihydrogen peroxide; potassium bromide In chloroform; water at 25℃; for 24h; Yield given. Yields of byproduct given;
With bromine; cyclomaltooctaose In tetrachloromethane at 0℃; for 0.5h;
1: 19 %Spectr. 2: 77 %Spectr. With sodium bromate; sulfuric acid; sodium bromide In dichloromethane; water at 20℃; for 8h;
1: 60 %Spectr. 2: 8 %Spectr. With sodium bromate; sulfuric acid; sodium bromide In water; dimethyl sulfoxide at 20℃; for 8h;
With hydrogen bromide; dihydrogen peroxide In dichloromethane; water at 20℃; for 24h; Darkness;
With tetraethylammonium bromide; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione
1: 10 %Chromat. 2: 44 %Chromat. With Oxone; quartz; sodium bromide In n-heptane for 0.333333h; Milling; chemoselective reaction;
With perchloric acid; C12H18MoN2O5; dihydrogen peroxide; potassium bromide In water; acetonitrile at 24.84℃; for 1h;

Reference: [1]MacHarla, Arun Kumar; Chozhiyath Nappunni, Rohitha; Nama, Narender [Tetrahedron Letters, 2012, vol. 53, # 11, p. 1401 - 1405]
[2]Dewkar, Gajanan K.; Narina, Srinivasarao V.; Sudalai, Arumugam [Organic Letters, 2003, vol. 5, # 23, p. 4501 - 4504]
[3]Location in patent: experimental part Podgorsek, Ajda; Eissen, Marco; Fleckenstein, Jens; Stavber, Stojan; Zupan, Marko; Iskra, Jernej [Green Chemistry, 2009, vol. 11, # 1, p. 120 - 126]
[4]Agrawal, Manoj K.; Adimurthy, Subbarayappa; Ganguly, Bishwajit; Ghosh, Pushpito K. [Tetrahedron, 2009, vol. 65, # 14, p. 2791 - 2797]
[5]Location in patent: scheme or table MacHarla, Arun Kumar; Chozhiyath Nappunni, Rohitha; Nama, Narender [Tetrahedron Letters, 2012, vol. 53, # 11, p. 1401 - 1405]
[6]Qaseer [Polish Journal of Chemistry, 2007, vol. 81, # 1, p. 31 - 38]
[7]Location in patent: experimental part Zhang, Jinglei; Wang, Jie; Qiu, Zhuibai; Wang, Yang [Tetrahedron, 2011, vol. 67, # 36, p. 6859 - 6867]
[8]Seitz, Jakob; Wirth, Thomas [Organic and Biomolecular Chemistry, 2021, vol. 19, # 31, p. 6892 - 6896]
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[13]Location in patent: experimental part Patil, Rajendra D.; Joshi, Girdhar; Adimurthy, Subbarayappa; Ranu, Brindaban C. [Tetrahedron Letters, 2009, vol. 50, # 21, p. 2529 - 2532]
[14]Location in patent: experimental part Patil, Rajendra D.; Joshi, Girdhar; Adimurthy, Subbarayappa; Ranu, Brindaban C. [Tetrahedron Letters, 2009, vol. 50, # 21, p. 2529 - 2532]
[15]Location in patent: experimental part Podgoršek, Ajda; Stavber, Stojan; Zupan, Marko; Iskra, Jernej [Tetrahedron, 2009, vol. 65, # 22, p. 4429 - 4439]
[16]Location in patent: body text Deshmukh, Swapnil S.; Chaudhari, Kiran H.; Akamanchi, Krishnacharya G. [Synlett, 2011, # 1, p. 81 - 83]
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  • 3
  • [ 100-41-4 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
73% With N-Bromosuccinimide; In 1,2-dichloro-ethane; at 100℃; for 12h;Inert atmosphere; Under nitrogen, <strong>[100-41-4]ethylbenzene</strong> 1a (0.5 mmol), NBS (1.25 mmol) and DCE (2 mL) were added to the reaction tube. Stir at 100 C for 12 hours. After stopping the reaction, cool to room temperature, evaporate the solvent and separate by column chromatography. The volume ratio (mL / mL) of the eluent used is ethyl acetate: petroleum ether = 0: 100 ~ 1: 200 to obtain 1-phenyl- 1,2-dibromoethane 3a with a yield of 73%.
  • 4
  • [ 93-52-7 ]
  • [ 536-74-3 ]
YieldReaction ConditionsOperation in experiment
98% With potassium hydroxide In Petroleum ether at 80℃; for 1h;
97.5% With sodium methylate In tetrahydrofuran Reflux; 1-6 Example 2 Embodiment two: In a 500ml three-necked flask, add 160ml of tetrahydrofuran and 52.8g (0.2mol) of 1,2-dibromoethylbenzene,Sodium methoxide 22.68g (0.42mol),Stir well,Heat reflux to react to raw material 1,Residual 2-dibromoethylbenzene≦0.5%,After filtering, the filter cake is washed with tetrahydrofuran,The filtrates were then combined and distilled under reduced pressure,Phenylacetylene was obtained with a yield of 97.5%,The GC purity is 99.14%.
95% With 18-crown-6 ether; potassium <i>tert</i>-butylate In Petroleum ether at 25℃; for 0.5h;
84% With potassium hydroxide In hexane at 70℃; for 16h;
80% With potassium hydroxide at 80 - 90℃; for 4.5h;
79% With sodium amide In ammonia liquid NH3;
70.4% With potassium fluoride on basic alumina In various solvent(s) at 100℃; for 6h;
70% With potassium hydroxide In diethyl ether; water at 180 - 220℃;
58.4% With potassium hydroxide at 120 - 140℃; Green chemistry; 1-4 Example 3: In a 500ml three-necked flask, add 52.8g (0.2mol) of 1,2-dibromoethylbenzene, 100g of catalyst EB-D, 23.56g (0.42mol) of potassium hydroxide, stir and mix well, heat to 120140, After reacting until the raw material 1,2-dibromoethylbenzene remains ≦0.5%, the bromide is removed by filtration, and the filtrate is rectified to obtain phenylacetylene with a yield of 58.4% and a GC purity of 99.67%.
With ammonia; sodium amide; ferric nitrate
84 % Chromat. With potassium hydroxide In benzene at 70℃; for 1h;
80 % Chromat. With potassium hydroxide In hexane at 70℃; for 16h; three-phase cond.; var. solvents, var. temp., var. times, var. yields, var. catalysts;
86 % Chromat. With potassium hydroxide; Aliquat 336 In xylene Heating;
Multi-step reaction with 2 steps 1: potassium phosphate / ethanol / 0.17 h / 80 °C 2: potassium phosphate / ethanol / 80 °C

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[2]Current Patent Assignee: ZHUHAI GREAT COMPOSITE MAT - CN112457148, 2021, A Location in patent: Paragraph 0037-0048
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  • 5
  • [ 93-52-7 ]
  • [ 70-11-1 ]
YieldReaction ConditionsOperation in experiment
35% With 1-methyl-4-nitrosobenzene; sodium acetate In dichloromethane at 55℃; for 12h; chemoselective reaction;
With nitric acid
Multi-step reaction with 2 steps 1: water / acetone / 6 h / Reflux 2: N-Bromosuccinimide; water / 3 h / 80 °C / Inert atmosphere
  • 6
  • [ 93-52-7 ]
  • [ 98-81-7 ]
YieldReaction ConditionsOperation in experiment
92% With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 18h; Inert atmosphere; 2.3. General Procedure C: Elimination reaction to form SM/DA precursor. General procedure: For example the preparation of 1-(1-bromovinyl)-4-methylbenzene (1l)-1-(1,2-Dibromoethyl)-4-methylbenzene (300 mg, 1.08 mmol, 1 equiv) and K2CO3 (298 mg,2.16 mmol, 2 equiv) were weighed into an oven dried flask. The flask was sealed and purged N2, before the addition of THF (2.2 mL) and methanol (2.2 mL) (1:1, 0.25 M). The reactionmixture was stirred at room temperature for 6 h. After the reaction was complete, the reactionmixture was diluted in Et2O (20 mL) and washed with H2O (20 mL) and brine (20 mL). The organic phase was dried over Na2SO4, filtered, and concentrated under reduced pressure to afford the desired product as a pale yellow oil (209 mg, 98%), which was used immediatelyin subsequent reactions without further purification.
66% With potassium hydroxide
With sodium ethanolate In ethanol at 25℃; element effect;
With sodium hydroxide In 1,2-dimethoxyethane
With lithium diethylamide In diethyl ether at -50 - 20℃;
With potassium hydroxide
With sodium ethanolate In ethanol at 25℃;
With potassium phosphate; 1-butyl-3-methylimidazolium Tetrafluoroborate In 1,2-dimethoxyethane at 70℃; for 3h;
With potassium hydroxide In methanol
With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 3h;
With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 3h;
With potassium carbonate In tetrahydrofuran; methanol
With potassium carbonate In tetrahydrofuran; methanol at 20℃; Schlenk technique;

Reference: [1]Cain, David L.; McLaughlin, Calum; Molloy, John J.; Carpenter-Warren, Cameron; Anderson, Niall A.; Watson, Allan J. B. [Synlett, 2019, vol. 30, # 7, p. 787 - 791]
[2]Larock, R. C.; Varaprath, S.; Lau, H. H.; Fellows, C. A. [Journal of the American Chemical Society, 1984, vol. 106, # 18, p. 5274 - 5284]
[3]Koch, Heinz F.; McLennan, Duncan J.; Koch, Judith G.; Tumas, William; Dobson, Brian; Koch, Nanci H. [Journal of the American Chemical Society, 1983, vol. 105, # 7, p. 1930 - 1937]
[4]Tarchini,C. et al. [Helvetica Chimica Acta, 1979, vol. 62, p. 635 - 640]
[5]Reisdorf,D.; Normant,H. [Organometallics in Chemical Synthesis, 1972, vol. 1, p. 375 - 391]
[6]Georgian,V.; Lepe M.,J. [Journal of Organic Chemistry, 1964, vol. 29, p. 45 - 50] Brewster,J.H.; Bayer,H.O. [Journal of Organic Chemistry, 1964, vol. 29, p. 105 - 110] Hanzlik,R.P.; Hilbert,J.M. [Journal of Organic Chemistry, 1978, vol. 43, # 4, p. 610 - 614]
[7]Koch, Heinz F.; Lodder, Gerrit; Koch, Judith G.; Bogdan, David J.; Brown, Geoffrey H.; Carlson, Carrie A.; Dean, Amy B.; Hage, Ronald; Han, Patrick; Hopman, Johan C. P.; James, Lisa A.; Knape, Petra M.; Roos, Eric C.; Sardina, Melissa L.; Sawyer, Rachael A.; Scott, Barbara O.; Testa III, Charles A.; Wickham, Steven D. [Journal of the American Chemical Society, 1997, vol. 119, # 42, p. 9965 - 9974]
[8]Tikhonov; Vasil'ev; Chirskaya; Struchkova; Merkulova; Zlotin [Russian Chemical Bulletin, 2007, vol. 56, # 1, p. 122 - 129]
[9]Takenaka, Katsuhiko; Amamoto, Shuhei; Kishi, Hiroto; Takeshita, Hiroki; Miya, Masamitsu; Shiomi, Tomoo [Macromolecules, 2013, vol. 46, # 18, p. 7282 - 7289]
[10]Piou, Tiffany; Rovis, Tomislav [Journal of the American Chemical Society, 2014, vol. 136, # 32, p. 11292 - 11295] Zhang, Yu; Liu, Haidong; Tang, Luning; Tang, Hai-Jun; Wang, Lu; Zhu, Chuan; Feng, Chao [Journal of the American Chemical Society, 2018, vol. 140, # 34, p. 10695 - 10699]
[11]Phipps, Erik J. T.; Rovis, Tomislav [Journal of the American Chemical Society, 2019] Phipps, Erik J.T.; Rovis, Tomislav [Journal of the American Chemical Society, 2019, vol. 141, # 17, p. 6807 - 6811]
[12]Phipps, Erik J. T.; Piou, Tiffany; Rovis, Tomislav [Synlett, 2019, vol. 30, # 15, p. 1787 - 1790]
[13]Wang, Zhixin; Li, Yang; Chen, Fan; Qian, Peng-Cheng; Cheng, Jiang [Chemical Communications, 2021, vol. 57, # 14, p. 1810 - 1813]
  • 7
  • [ 93-52-7 ]
  • [ 16717-64-9 ]
YieldReaction ConditionsOperation in experiment
92% With Caswell No. 744A In N,N-dimethyl-formamide at 20℃; for 24h;
90% With Caswell No. 744A In N,N-dimethyl-formamide at 24℃; for 20h;
90% With Caswell No. 744A In N,N-dimethyl-formamide at 20℃; for 24h;
90% With Caswell No. 744A In N,N-dimethyl-formamide at 20℃;
86% With Caswell No. 744A In N,N-dimethyl-formamide at 20℃;
80% With Caswell No. 744A In N,N-dimethyl-formamide at 20℃; for 24h;
80% With Caswell No. 744A In N,N-dimethyl-formamide at 20℃; Inert atmosphere;
57% With Caswell No. 744A In N,N-dimethyl-formamide at 25℃; for 24h; Schlenk technique;
(i) NaN3, DMF, (ii) KOtBu, benzene; Multistep reaction;
(i) NaN3, (ii) aq. NaOH; Multistep reaction;
With Caswell No. 744A In N,N-dimethyl-formamide at 0℃; for 14h;
Multi-step reaction with 2 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13.75 h / 25 °C 2: sodium hydroxide / lithium hydroxide monohydrate; dimethyl sulfoxide / 0.4 h / 25 °C / Inert atmosphere
Stage #1: 1-(1,2-dibromoethyl)benzene With Caswell No. 744A In dimethyl sulfoxide at 15 - 20℃; for 13h; Inert atmosphere; Stage #2: With sodium hydroxide In lithium hydroxide monohydrate; dimethyl sulfoxide at 12 - 20℃; for 24h; Inert atmosphere;
With Caswell No. 744A In N,N-dimethyl-formamide at 20℃; for 3h;
Stage #1: 1-(1,2-dibromoethyl)benzene With Caswell No. 744A In dimethyl sulfoxide at 0 - 20℃; for 14h; Stage #2: With sodium hydroxide In lithium hydroxide monohydrate at 20℃; for 24h;
Multi-step reaction with 2 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13.75 h / 25 °C 2: sodium hydroxide / lithium hydroxide monohydrate / 24 h / 25 °C
Multi-step reaction with 2 steps 1: Caswell No. 744A / dimethyl sulfoxide / 0.75 h / 20 °C 2: sodium hydroxide; lithium hydroxide monohydrate / 1 h / 20 °C
With Caswell No. 744A In N,N-dimethyl-formamide at 20℃; Inert atmosphere;
With Caswell No. 744A; sodium hydroxide In dimethylsulfoxide-d6; lithium hydroxide monohydrate at 20℃; for 24h; Inert atmosphere; 2.1 The white solid (1) was dissolved in 140 mL of DMSO.9.8 g (150 mmol) of sodium azide was added under nitrogen.Stir at room temperature overnight.Then 4 mL of an aqueous solution containing 4 g of sodium hydroxide was added to the mixture.Stirring was continued for 24 h.The reaction product was poured into 400 mL of 2% (wt%) sodium bicarbonate solution.Extracted with dichloromethane,The organic layer is washed repeatedly,After drying, it was evaporated to a dark red oil.After separation by a silica gel column (solvent petroleum ether), a pale yellow oil (2) was obtained.
With Caswell No. 744A; sodium hydroxide In dimethylsulfoxide-d6; lithium hydroxide monohydrate at 20℃; for 24h; Inert atmosphere; 2.1 The white solid (1) was dissolved in 140 mL of DMSO.9.8 g (150 mmol) of sodium azide was added under nitrogen.Stir at room temperature overnight.Then 4 mL of an aqueous solution containing 4 g of sodium hydroxide was added to the mixture.Stirring was continued for 24 h.The reaction product was poured into 400 mL of 2% (wt%) sodium bicarbonate solution.Extracted with dichloromethane,The organic layer is washed repeatedly,After drying, it was evaporated to a dark red oil.After separation by a silica gel column (solvent petroleum ether), a pale yellow oil (2) was obtained.
Multi-step reaction with 2 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13 h / 20 °C / Inert atmosphere 2: sodium hydroxide / 24 h / 20 °C
With Caswell No. 744A In N,N-dimethyl-formamide for 5h;
With Caswell No. 744A
Multi-step reaction with 2 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13.45 h / 20 °C / Inert atmosphere 2: sodium hydroxide / dimethyl sulfoxide; lithium hydroxide monohydrate / 24 h / 20 °C
With Caswell No. 744A In N,N-dimethyl-formamide at 20℃;
With Caswell No. 744A In N,N-dimethyl-formamide
With Caswell No. 744A In N,N-dimethyl-formamide at 20℃; for 10h; 1.1 (1) Synthesis of 3-phenyl-2H-azacyclopropene The raw material (1,2-dibromoethyl)benzene (5.2g, 19.9mmol) was dissolved in DMF (30ml), sodium azide (3.9g, 60mmol) was slowly added to the above solution, and reacted at room temperature for 10h . Then, it was extracted three times with anhydrous ether and saturated sodium carbonate solution, and the organic phase was combined and concentrated to obtain (1-azidovinyl)benzene;
With Caswell No. 744A In N,N-dimethyl-formamide at 20℃; General procedure: For the synthesis of vinyl azides, the corresponding styrene (3 g) was dissolved in DCM (10 mL) and the mixture was cooled to 0°C. Bromine (1 eq) was dissolved in DCM (10 mL) and was added dropwise to the styrene solution under magnetic stirring at 0°C. Then, the reaction mixture was stirred for 1 h at room temperature. A saturated solution of Na2S2O3 was added until the colour of bromine faded. The resulting mixture was washed with water (2×10 mL). The organic layer was dried over Na2SO4, and the solvent was removed under reduced pressure. The resulting dibromide was dissolved in DMF (20 mL) and NaN3 (3 eq) was added under magnetic stirring. The reaction mixture was stirred overnight at room temperature. Then, it was diluted with water (20 mL) and was washed with Et2O (3×10 mL). The organic layer was dried over Na2SO4, and the solvent was removed under reduced pressure. The residue was purified using column chromatography (eluent - PE) to give pure vinyl azide.
With Caswell No. 744A In N,N-dimethyl-formamide at 100℃; Inert atmosphere;
With Caswell No. 744A
Multi-step reaction with 2 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13 h / 25 °C / Inert atmosphere 2: sodium hydroxide / lithium hydroxide monohydrate / 24 h / 25 °C

Reference: [1]Xiang, Likui; Niu, Yanning; Pang, Xiaobo; Yang, Xiaodong; Yan, Rulong [Chemical Communications, 2015, vol. 51, # 30, p. 6598 - 6600]
[2]Cen, Jinghe; Li, Jianxiao; Zhang, Yu; Zhu, Zhongzhi; Yang, Shaorong; Jiang, Huanfeng [Organic Letters, 2018, vol. 20, # 15, p. 4434 - 4438]
[3]Cen, Jinghe; Wu, Yaodan; Li, Jianxiao; Huang, Liangbin; Wu, Wanqing; Zhu, Zhongzhi; Yang, Shaorong; Jiang, Huanfeng [Organic Letters, 2019, vol. 21, # 7, p. 2090 - 2094]
[4]Nie, Biao; Wu, Wanqing; Ren, Qingyun; Wang, Zhongqing; Zhang, Ji; Zhang, Yingjun; Jiang, Huanfeng [Organic Letters, 2020, vol. 22, # 20, p. 7786 - 7790]
[5]Jiang, Huanfeng; Nie, Biao; Ren, Qingyun; Wu, Wanqing; Zeng, Wei; Zhang, Ji; Zhang, Yingjun [Advanced synthesis and catalysis, 2020]
[6]Donthiri, Ramachandra Reddy; Pappula, Venkatanarayana; Reddy, N. Naresh Kumar; Bairagi, Dipayan; Adimurthy, Subbarayappa [Journal of Organic Chemistry, 2014, vol. 79, # 22, p. 11277 - 11284]
[7]Loy, Nicole S. Y.; Kim, Sunggak; Park, Cheol-Min [Organic Letters, 2015, vol. 17, # 3, p. 395 - 397]
[8]Qi, Zaojuan; Li, Weihe; Niu, Yanning; Benassi, Enrico; Qian, Bo [Organic Letters, 2021, vol. 23, # 7, p. 2399 - 2404]
[9]Smolinsky,G. [Journal of Organic Chemistry, 1962, vol. 27, p. 3557 - 3559]
[10]Hortmann,A.G. et al. [Journal of Organic Chemistry, 1972, vol. 37, # 2, p. 322 - 324]
[11]Chiba, Shunsuke; Wang, Yi-Feng; Lapointe, Guillaume; Narasaka, Koichi [Organic Letters, 2008, vol. 10, # 2, p. 313 - 316]
[12]Wang, Rui; Yu, Fabiao; Liu, Ping; Chen, Lingxin [Chemical Communications, 2012, vol. 48, # 43, p. 5310 - 5312]
[13]Jiang, Na; Fan, Jiangli; Liu, Tao; Cao, Jianfang; Qiao, Bo; Wang, Jingyun; Gao, Pan; Peng, Xiaojun [Chemical Communications, 2013, vol. 49, # 90, p. 10620 - 10622]
[14]Zhang, Guolin; Ni, Hangcheng; Chen, Wenteng; Shao, Jiaan; Liu, Huan; Chen, Binhui; Yu, Yongping [Organic Letters, 2013, vol. 15, # 23, p. 5967 - 5969]
[15]Zhao, Yun-Zhou; Yang, Hai-Bin; Tang, Xiang-Ying; Shi, Min [Chemistry - A European Journal, 2015, vol. 21, # 9, p. 3562 - 3566]
[16]Chen, Lili; Li, Hongji; Li, Pinhua; Wang, Lei [Organic Letters, 2016, vol. 18, # 15, p. 3646 - 3649]
[17]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES; Dalian Institute of Chemical Physics (in: CAS) - CN105669513, 2016, A
[18]Dey, Raghunath; Banerjee, Prabal [Organic Letters, 2017, vol. 19, # 2, p. 304 - 307]
[19]Current Patent Assignee: JIANGSU INST PARASITIC DISEASES - CN109006823, 2018, A Location in patent: Paragraph 0072; 0074; 0075; 0077
[20]Current Patent Assignee: JIANGSU INST PARASITIC DISEASES - CN109006824, 2018, A Location in patent: Paragraph 0080; 0082; 0085
[21]De, Aramita; Santra, Sougata; Hajra, Alakananda; Zyryanov, Grigory V.; Majee, Adinath [Journal of Organic Chemistry, 2019, vol. 84, # 18, p. 11735 - 11740]
[22]Zhou, Effie Y.; Knox, Hailey J.; Liu, Chang; Zhao, Weili; Chan, Jefferson [Journal of the American Chemical Society, 2019, vol. 141, # 44, p. 17601 - 17609]
[23]Mulina, Olga M.; Zhironkina, Nataliya V.; Paveliev, Stanislav A.; Demchuk, Dmitry V.; Terent'Ev, Alexander O. [Organic Letters, 2020, vol. 22, # 5, p. 1818 - 1824]
[24]De, Aramita; Majee, Adinath; Santra, Sougata; Zyryanov, Grigory V. [Organic Letters, 2020, vol. 22, # 10, p. 3926 - 3930]
[25]Paveliev, Stanislav A.; Churakov, Artem I.; Alimkhanova, Liliya S.; Segida, Oleg O.; Nikishin, Gennady I.; Terent'ev, Alexander O. [Advanced Synthesis and Catalysis, 2020, vol. 362, # 18, p. 3864 - 3871]
[26]Shrestha, Pradeep; Dissanayake, Komadhie C.; Gehrmann, Elizabeth J.; Wijesooriya, Chamari S.; Mukhopadhyay, Atreyee; Smith, Emily A.; Winter, Arthur H. [Journal of the American Chemical Society, 2020, vol. 142, # 36, p. 15505 - 15512]
[27]Current Patent Assignee: FUDAN UNIVERSITY - CN112010880, 2020, A Location in patent: Paragraph 0042-0045
[28]Mulina, Olga M.; Ilovaisky, Alexey I.; Opatz, Till; Terent'ev, Alexander O. [Tetrahedron Letters, 2021, vol. 64]
[29]Yadav, Anuj K.; Tapia Hernandez, Rodrigo; Chan, Jefferson [Methods in Enzymology, 2021, vol. 657, p. 415 - 441]
[30]Mulina, Olga M.; Doronin, Mikhail M.; Terent'ev, Alexander O. [Tetrahedron Letters, 2021, vol. 84]
[31]Balalaie, Saeed; Hosseinijei, Reyhaneh; Nikbakht, Ali; Rominger, Frank; Zahedian Tejeneki, Hossein [Organic and Biomolecular Chemistry, 2022, vol. 20, # 15, p. 3076 - 3080]
  • 8
  • [ 100-42-5 ]
  • [ 7182-86-7 ]
  • Toluene-4-sulfonic acid 2-bromo-2-phenyl-ethyl ester [ No CAS ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
With bromine In dichloromethane Ambient temperature;
  • 9
  • [ 100-42-5 ]
  • Tetramethylenebromoselenonium bromide [ No CAS ]
  • [ 114310-83-7 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 83% 2: 17% With selenolane In acetonitrile at 20℃; for 24h;
  • 10
  • [ 100-42-5 ]
  • [ 87767-94-0 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 72% 2: 21% With lead(IV) acetate; zinc dibromide In acetic acid for 0.166667h; Ambient temperature;
  • 12
  • [ 292638-84-7 ]
  • [ 1786-36-3 ]
  • [ 55153-06-5 ]
  • [ 102921-26-6 ]
  • 13
  • [ 542-92-7 ]
  • [ 93-52-7 ]
  • [ 13189-30-5 ]
YieldReaction ConditionsOperation in experiment
65% With potassium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In dichloromethane at 30 - 35℃; for 4h;
  • 14
  • [ 93-52-7 ]
  • [ 100-42-5 ]
YieldReaction ConditionsOperation in experiment
95% With bismuth(III) chloride; indium In methanol at 20℃; for 0.5h; Sonication; chemoselective reaction;
95% With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; sodium carbonate In dimethyl sulfoxide at 20℃; for 1.5h; Inert atmosphere; Irradiation;
94% With 1,1'-bis(trimethylsilyl)-1,1',4,4'-tetrahydro-4,4'-bipyridylidene In acetonitrile at 20℃; for 2h; Inert atmosphere;
94% With 1,1'-bis(trimethylsilyl)-1,1',4,4'-tetrahydro-4,4'-bipyridylidene In acetonitrile at 20℃; for 2h; Inert atmosphere;
86% With sodium sulfide In N,N-dimethyl-formamide for 3h; Ambient temperature;
84% With sodium dithionite; potassium carbonate In dichloromethane; water for 2.5h; Ambient temperature;
80% With potassium graphite In benzene for 8h; Ambient temperature; vic-debromination by intercalate, influence of solvent;
78.8% With tellurium; sodium diethyl phosphite In ethanol for 8h; Ambient temperature;
70% With thiourea; zinc In diphenylether at 110℃;
70% With tributylstibine at 100℃; for 4h;
57% With N,N,N,N,-tetramethylethylenediamine; sexithiophene In N,N-dimethyl-formamide for 3h; Inert atmosphere; Irradiation;
With tetraethylammonium perchlorate In dimethyl sulfoxide at 20℃; electrocatalytic reduction;
85 % Chromat. With bis(cyclopentadienyl)titanium dichloride; zinc In tetrahydrofuran
With bis(triphenylstannyl)tellurium In [D3]acetonitrile for 3h; Ambient temperature; Yield given;
With water-d2; sodium iodide at 60℃; for 4h; Sonication;

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  • 15
  • [ 93-52-7 ]
  • [ 103-63-9 ]
YieldReaction ConditionsOperation in experiment
81% With zinc(II) tetrahydroborate In diethyl ether for 24h; Ambient temperature;
  • 16
  • [ 93-52-7 ]
  • [ 100-42-5 ]
  • [ 3489-31-4 ]
YieldReaction ConditionsOperation in experiment
1: 7% 2: 78% With sodium trithiocarbonate In water; benzene at 50℃; for 1h;
  • 18
  • [ 170033-45-1 ]
  • [ 93-52-7 ]
  • 5-Methyl-2,7-diphenyl-2,3-dihydro-5H-1-thia-3a,5,6-triaza-azulene-4-thione [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In benzene for 6h; Ambient temperature;
  • 20
  • [ 93-52-7 ]
  • [ 100-42-5 ]
  • [ 3489-31-4 ]
YieldReaction ConditionsOperation in experiment
1: 78% 2: 7% In water; benzene at 50℃; for 1h;
  • 21
  • [ 110-86-1 ]
  • [ 93-52-7 ]
  • 1-(2-Bromo-1-phenylethyl)pyridinium perchlorate [ No CAS ]
  • 1-(1-Phenylvinyl)pyridinium perchlorate [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 84% 2: 10% Stage #1: pyridine; (1,2-dibromoethyl)benzene With pyridine In acetonitrile for 6h; Heating; Stage #2: With perchloric acid; water
  • 22
  • [ 100-42-5 ]
  • [ 96-09-3 ]
  • [ 6622-78-2 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
80 % Chromat. With sodium hypochlorite; potassium bromide In phosphate buffer; acetonitrile at 40℃; for 1h;
  • 23
  • [ 100-42-5 ]
  • [ 2425-28-7 ]
  • [ 64342-39-8 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 30% 2: 10% 3: 1% With ammonium cerium(IV) nitrate; 1-butyl-3-methylimidazolium Tetrafluoroborate; potassium bromide In water at 20℃;
  • 24
  • [ 5720-07-0 ]
  • [ 93-52-7 ]
  • [ 4333-75-9 ]
  • [ 1694-19-5 ]
YieldReaction ConditionsOperation in experiment
1: 94 % Chromat. 2: 6 % Chromat. Stage #1: (1,2-dibromoethyl)benzene With potassium hydroxide In tetrahydrofuran at 100℃; for 1h; Stage #2: 4-methoxyphenylboronic acid With palladium diacetate; triphenylphosphine In tetrahydrofuran; methanol at 100℃; for 1h;
  • 25
  • [ 100-42-5 ]
  • [ 67-56-1 ]
  • [ 13685-00-2 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
57% With sodium periodate; sulfuric acid; lithium bromide In water at 25℃;
  • 26
  • [ 100-42-5 ]
  • [ 98-81-7 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 75% 2: 13% With sol-gel entrapped pyridinium hydrobromide perbromide; silica gel; 1,5,7-triazabicyclo[4.4.0]decane In hexane at 65℃; for 12h;
  • 27
  • [ 89694-48-4 ]
  • [ 93-52-7 ]
  • 4-chloro-1-methoxy-2-(1-phenylvinyl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide; triphenylphosphine In tetrahydrofuran at 20 - 100℃;
  • 28
  • [ 1822-66-8 ]
  • [ 93-52-7 ]
  • 2-phenyl-2,3-dihydro-thieno[3,4-<i>b</i>][1,4]dioxine-5,7-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
27% With triethylamine In N,N-dimethyl-formamide at 90℃; for 20h;
  • 29
  • [ 100-42-5 ]
  • [ 29847-04-9 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
85% With N-Bromosuccinimide; trimethylsilylazide; 4 A molecular sieve In dichloromethane at 0℃; for 0.166667h;
  • 30
  • [ 100-42-5 ]
  • [ 95-47-6 ]
  • [ 40231-29-6 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
43% With N-Bromosuccinimide; 4 A molecular sieve; sodium hydrogencarbonate In acetonitrile at 25℃; for 12h;
  • 31
  • [ 100-42-5 ]
  • [ 108-88-3 ]
  • [ 40231-27-4 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
40% With N-Bromosuccinimide; 4 A molecular sieve; sodium hydrogencarbonate In acetonitrile at 25℃; for 12h;
  • 32
  • [ 873-55-2 ]
  • [ 93-52-7 ]
  • [ 16212-06-9 ]
YieldReaction ConditionsOperation in experiment
65% With triethylamine In N,N,N,N,N,N-hexamethylphosphoric triamide at 80℃; for 10h;
  • 33
  • [ 93-52-7 ]
  • [ 4072-28-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: potassium hydroxide; PPh3 / Pd(OAc)2 / tetrahydrofuran / 20 - 100 °C 2: 44 percent / gold(I) chloride; tert-butyl hydroperoxide; neocuproine / H2O; 2-methyl-propan-2-ol / 3 h / 90 °C
  • 34
  • [ 93-52-7 ]
  • 2-methyl-4-phenylbutan-1-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 21 percent / pyridine / 4 h / Heating 2: 1.) bis(dimethylglyoximato)(pyridine)cobalt(I) / 1.) MeOH, RT, 6 h, 2.) benzene, irradiation 3: H2 / Pd/C / ethanol
Multi-step reaction with 3 steps 1: 21 percent / pyridine / 4 h / Heating 2: 1.) bis(dimethylglyoximato)(pyridine)cobalt(I) / 1.) MeOH, RT, 6 h, 2.) CHCl3, irradiation 3: H2 / Pd/C / ethanol
  • 35
  • NiCl2 (Ph2 P(CH)3 PPh2) [ No CAS ]
  • [ 100-39-0 ]
  • [ 93-52-7 ]
  • 1-benzyl-3-vinylbenzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% In tetrahydrofuran Another Synthesis of (3-Vinylphenyl)phenylmethane Another Synthesis of (3-Vinylphenyl)phenylmethane To a 2 liter three-neck flask equipped with a reflux condenser and a stirrer were added 28 g (1.15 moles) of metallic magnesium and 50 ml of tetrahydrofuran dried with sodium metal and it was stirred at room temperature. A solution of 183 g of 3-vinylbenzene bromide (1.02 moles) in 500 ml of dry tetrahydrofuran was dropped slowly over 2 hours. The reaction temperature was kept at 80° C. After the dropping, it was stirred for further 1 hour at 80° C. The thus obtained Grignard reagent was dropped slowly over 2 hours to a solution of 171 g (1.0 mole) of benzyl bromide and 5.5 g of NiCl2 (Ph2 P(CH)3 PPh2) in 500 ml of dry ether and the stirring was continued for further 1 hour at 35° C. The reaction mixture was then poured into ice water. After that, it was put into the separatory funnel to recover an oily layer and ether and tetrahydrofuran were evaporated off under reduced pressure. Thereby obtaining (3-vinylphenyl)phenylmethane in a yield of 60%. The analytical data on the thus obtained product are shown in the following: Boiling Point: 108.5-110.5° C./0.5-1 mmHg IR: (Neat) cm-1 3040, 2930, 1635, 1600, 1500, 1460, 995, 910, 790, 710, 700 1 H-NMR: (CCl4, δ ppm): 6.70-7.70, (9H Multiplet), 6.30-6.60, (1H Quadruplet), 5.40-5.70, (1H Doublet), 5.00-5.15, (1H Doublet), 3.80, (2H Singlet). Elemental Analysis: (as C15 H14) Calculated: C: 92.78%, H: 7.22%, Found: C: 92.80%, H: 7.20%.
  • 36
  • [ 68-12-2 ]
  • [ 1004-39-3 ]
  • [ 102921-26-6 ]
  • 7-Amino-2-phenyl-5-imino-2,3-dihydro-5H-thiazolo[3,2-a]pyrimidine-hydrobromide [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With potassium carbonate; Example 4 7-Amino-2-phenyl-5-imino-2,3-dihydro-5H-thiazolo[3,2-a]pyrimidine-hydrobromide A mixture of 14.2 g (0.1 mole) of 2-mercapto-4,6-diamino-pyrimidine, 30.4 g (0.115 mole) of (1,2-dibromo-ethyl)-benzene, 200 ml of dimethyl formamide and 13.8 g (0.1 mole) of potassium carbonate is stirred at 45 C. for 6 hours. The reaction mixture is cooled, the precipitate is filtered, washed with water and dried. Thus 26.0 g of the desired compound are obtained, yield 80%, m.p.: above 300 C.
  • 37
  • [ 84338-83-0 ]
  • [ 93-52-7 ]
  • ethyl 8-chloro-7-fluoro-5-oxo-1-phenyl-1,2-dihydro-5H-thiazolo(3,2-a)quinoline-4-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate In water; N,N-dimethyl-formamide 7 Ethyl 8-chloro-7-fluoro-5-oxo-1-phenyl-1,2-dihydro-5H-thiazolo(3,2-a)quinoline-4-carboxylate EXAMPLE 7 Ethyl 8-chloro-7-fluoro-5-oxo-1-phenyl-1,2-dihydro-5H-thiazolo(3,2-a)quinoline-4-carboxylate In dimethyl formamide was dissolved 2.0 grams (6.6 mmol) of ethyl 7-chloro-6-fluoro-4-hydroxy-2-mercaptoquinoline-3-carboxylate and the mixture was heated at 40° C. for four hours with stirring after addition of 1.8 grams (13.2 mmol) of potassium carbonate and 2.1 grams (8.0 mmol) of (1,2-dibromoethyl)benzene. The content was concentrated under reduced pressure, water was added to the residue, extracted with chloroform, the chloroform extract was washed with water, dried, concentrated, and the resulting crystals were recrystallized from a mixture of chloroform and ether to give the title compound. The yield was 2.17 grams (81.3 percent) and the melting point was 172° C. Elementary analysis calculated as C20 H15 ClFNO3 S: C 59.48, H 3.84, N 3.47; Found: C 59.54, H 3.53, N 3.27.
  • 38
  • [ 134469-07-1 ]
  • [ 93-52-7 ]
  • [ 87215-81-4 ]
YieldReaction ConditionsOperation in experiment
In <i>N</i>-methyl-acetamide 3 2,3-Dihydro-2-phenylthiazolo[3,2-a]benzimidazole EXAMPLE 3 2,3-Dihydro-2-phenylthiazolo[3,2-a]benzimidazole (1,2-Dibromoethyl)benzene (21 g) was treated with 2-mercaptobenzimidazole (17 g) in dimethylformamide (100 ml) and the mixture was heated at 100° C. for 36 hours. On cooling, the solid material was removed by filtration and recrystallized from methanol and ethyl acetate to give the title compound as the hydrobromide salt (13.68 g). mp 207°-210° C. Analysis: Found: C, 53.8; H, 4.1; N, 8.5. C15 H12 N2 S.HBr requires C, 54.1; H, 3.9; N, 8.4%.
  • 39
  • [ 98-86-2 ]
  • [ 93-52-7 ]
  • [ 118064-64-5 ]
YieldReaction ConditionsOperation in experiment
89% (acetophenone basis) With ammonium chloride In tetrahydrofuran 1 Synthesis of 1-(3-vinylphenyl)-1-phenylethylene (formula I)-(1) Example 1 Synthesis of 1-(3-vinylphenyl)-1-phenylethylene (formula I)-(1) To a 2 liter three-neck flask equipped with a dropping funnel, a reflux condenser and a stirrer was added 25.5 g (1.05 mole) of metallic magnesium and it was dried sufficiently by supplying dry nitrogen gas. After that, 50 ml of tetrahydrofuran which had been dried with a molecular sieve 5 A, was put into the flask and the contents were stirred vigorously. A solution of 183 g (1.0 mole) of 3-vinylbenzene bromide in 500 ml of dried tetrahydrofuran was dropped little by little over 2 hours. The reaction temperature was maintained at 75° to 80° C. and, after the addition of the solution, the stirring was continued for further 1 hour as it stands. Into the thus obtained Grignard reagent of 3-vinylphenylmagnesium bromide (formula VII), a solution of 122.6 g (1.02 mole) of acetophenone (formula VIII) in 500 ml of dried tetrahydrofuran was dropped little by little for 2 hours. The reaction temperature was maintained at 75° to 80° C. and, after the dropping, the stirring was continued for further 1 hour as it stands. The reaction mixture was then poured into 3 liter of an aqueous solution of 75 g of ammonium chloride and it was left to stand still for 20 hours and an oily layer was recovered to obtain 1-(3-vinylphenyl)-1-phenylethyl alcohol (VPA: formula V) in a yield of 89% (acetophenone basis) by distilling off the tetrahydrofuran.
89% (acetophenone basis) With ammonium chloride In tetrahydrofuran 1 Synthesis of 1-(3-vinylphenyl)-1-phenylethylene (formula I) - (1) Example 1 Synthesis of 1-(3-vinylphenyl)-1-phenylethylene (formula I) - (1) To a 2 liter three-neck flask equipped with a dropping funnel, a reflux condenser and a stirrer was added 25.5 g (1.05 mole) of metallic magnesium and it was dried sufficiently by supplying dry nitrogen gas. After that, 50 ml of tetrahydrofuran which had been dried with a molecular sieve 5A, was put into the flask and the contents were stirred vigorously. A solution of 183 g (1.0 mole) of 3-vinylbenzene bromide in 500 ml of dried tetrahydrofuran was dropped little by little over 2 hours. The reaction temperature was maintained at 75 to 80°C and, after the addition of the solution, the stirring was continued for further 1 hour as it stands. Into the thus obtained Grignard reagent of 3-vinylphenylmagnesium bromide (formula VII), a solution of 122.6 g (1.02 mole) of acetophenone (formula VIII) in 500 ml of dried tetrahydrofuran was dropped little by little for 2 hours. The reaction temperature was maintained at 75 to 80°C and, after the dropping, the stirring was continued for further 1 hour as it stands. The reaction mixture was then poured into 3 liter of an aqueous solution of 75 g of ammonium chloride and it was left to stand still for 20 hours and an oily layer was recovered to obtain 1-(3-vinylphenyl)-1-phenylethyl alcohol (VPA: formula V) in a yield of 89% (acetophenone basis) by distilling off the tetrahydrofuran.
  • 40
  • ligands of 1,3-bis(diphenylphosphino)propane [ No CAS ]
  • [ 672-65-1 ]
  • [ 93-52-7 ]
  • 1-(3-vinylphenyl)-1-phenylethane [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% In tetrahydrofuran; water 2 Synthesis of 1-(3-vinylphenyl)-1-phenylethane (formula II) Example 2 Synthesis of 1-(3-vinylphenyl)-1-phenylethane (formula II) To a 2 liter three-neck flask equipped with a 500 ml dropping funnel, a reflux condenser, and a stirrer was added 28 g (1.15 mole) of metallic magnesium and it was dried sufficiently by supplying dry nitrogen gas. After that, 50 ml of tetrahydrofuran which had been dried with a molecular sieve 5 A, was dropped into the flask and the contents were stirred vigorously. A solution of 183 g (1.0 mole) of 3-vinylbenzene bromide in 500 ml of dry tetrahydrofuran was dropped little by little over 2 hours. The temperature was maintained at about 80° C. and, after the dropping of the solution, the stirring was continued for further 1 hour as it stands. Thereby obtaining a Grignard reagent (3-vinylphenylmagnesium bromide: formula VII). Then, 94 g (0.67 mole) of (1-chloroethyl)benzene of the formula (VI) and 5.4 g of the catalyst of nickel chloride (II) with ligands of 1,3-bis(diphenylphosphino)propane were mixed into 500 ml of dried ether. The above Grignard reagent was dropped little by little into this mixture over 2 hours. During the dropping, the temperature in the reactor was maintained at 0° C. After the dropping, stirring was continued for further 24 hours. The reaction mixture was then poured into iced water (1000 g of ice and 500 g of water) and aqueous layer and oily layer were separated to recover the oily layer. After that, ether and tetrahydrofuran were evaporated off under a reduced pressure to obtain 1-(3-vinylphenyl)-1-phenylethane in a yield of 74%.
  • 41
  • ligands of 1,3-bis(diphenylphosphino)-propane [ No CAS ]
  • [ 672-65-1 ]
  • [ 93-52-7 ]
  • 1-(3-vinylphenyl)-1-phenylethane [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% In tetrahydrofuran; water 2 Synthesis of 1-(3-vinylphenyl)-1-phenylethane (formula II) Example 2 Synthesis of 1-(3-vinylphenyl)-1-phenylethane (formula II) To a 2 liter three-neck flask equipped with a 500 ml dropping funnel, a reflux condenser, and a stirrer was added 28 g (1.15 mole) of metallic magnesium and it was dried sufficiently by supplying dry nitrogen gas. After that, 50 ml of tetrahydrofuran which had been dried with a molecular sieve 5A, was dropped into the flask and the contents were stirred vigorously. A solution of 183 g (1.0 mole) of 3-vinylbenzene bromide in 500 ml of dry tetrahydrofuran was dropped little by little over 2 hours. The temperature was maintained at about 80°C and, after the dropping of the solution, the stirring was continued for further 1 hour as it stands. Thereby obtaining a Grignard reagent (3-vinylphenylmagnesium bromide: formula VII). Then, 94 g (0.67 mole) of (1-chloroethyl)benzene or the formula (VI) and 5.4 g of the catalyst of nickel chloride (II) with ligands of 1,3-bis(diphenylphosphino)-propane were mixed into 500 ml of dried ether. The above Grignard reagent was dropped little by little into this mixture over 2 hours. During the dropping, the temperature in the reactor was maintained at 0°C. After the dropping, stirring was continued for further 24 hours. The reaction mixture was then poured into iced water (1000 a of ice and 500 g of water) and aqueous layer and oily layer were separated to recover the oily layer. After that, ether and tetrahydrofuran were evaporated under a reduced pressure to obtain 1-(3-vinylphenyl)-1-phenylethane in a yield of 74%. The analytical data on the product are shown in the following: Boiling Point: 123.5 - 125.0°C/(0.5-1.0 mmHg) 0.7 x 10-3 -1.3 x 10-3 bar IR: (Neat) cm-1
  • 42
  • [ 100-42-5 ]
  • [ 2425-28-7 ]
  • [ 70-11-1 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 64% 2: 9% 3: 24% With (2S,3S)-3-hydroxy-2-(4-methylphenylsulfonamido)butanoic acid; water; N-bromoacetamide In <i>tert</i>-butyl alcohol at 20℃; for 42h; regioselective reaction; 4.3. General procedure for the synthesis of bromohydrins with AcNHBr General procedure: NTsLT (6) (273 mg, 1 mmol) was dissolved in t-BuOH/H2O (1:1, 4 mL), then AcNHBr (19) (165 mg, 1.2 mmol) and olefin (1 mmol) were added to the solution. The mixture was stirred at room temperature. When the yellow color of the mixture faded, the reaction was complete (also monitored by TLC). Na2SO3 (50 mg) was added to the mixture, then extracted with ethyl acetate (3×10 mL) and the organic phases were washed with brine (10 mL) and dried over Na2SO4. The solvent was removed under reduced pressure and the crude residue was further purified by column chromatography to obtain the corresponding bromohydrin products.
1: 60% 2: 12% 3: 1% With sodium bromate; sulfuric acid; sodium bromide In 1,4-dioxane; water at 20℃; for 6.5h;
1: 40% 2: 36% 3: 10% With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione In 1,4-dioxane; water at 40℃; for 12h;
1: 39 %Spectr. 2: 24 %Spectr. 3: 3 %Spectr. With sodium bromate; sulfuric acid; sodium bromide In tetrahydrofuran; water at 20℃; for 8h;
1: 52 %Spectr. 2: 3 %Spectr. 3: 36 %Spectr. With N-Bromosuccinimide; water In 1,4-dioxane at 20℃; for 8h;
With hydrogen bromide; dihydrogen peroxide In water at 20℃; for 24h; Darkness;
1: 15.1 %Chromat. 2: 67.4 %Chromat. 3: 17.5 %Chromat. With tetrabutylammomium bromide; hydrogen bromide; dihydrogen peroxide In water at 0℃; for 52h;
1: 52.7 %Chromat. 2: 20.8 %Chromat. 3: 26.5 %Chromat. With hydrogen bromide; dihydrogen peroxide In hexane; water at 90℃; for 8h;
1: 28.6 %Chromat. 2: 5.2 %Chromat. 3: 66.2 %Chromat. With hydrogen bromide; dihydrogen peroxide In cyclohexane; water at 90℃; for 7.5h;
1: 75 %Chromat. 2: 10 %Chromat. 3: 15 %Chromat. With ammonium metavanadate; perchloric acid; tetrabutylammomium bromide; dihydrogen peroxide In chloroform; water at 20℃; for 0.5h; General bromination with TBAB General procedure: NH4VO3 (5 mol%) and H2O2 (200 mol%) were placed in a flask. After complete dissolution of the catalyst, TBAB (3 mmol) was added and the mixture was stirred at room temperature. Then, Et2O (10 ml) and aromatic substrate (1 mmol) were added to the mixture. Finally, by slow drip, 1 ml of 1N HClO4 solution was added. After adding the acid, the colour of the reaction changed from yellow to red due to the formation of oxomonoperoxovanadium. Conversion was followed by TLC and determined by GC. The phases were separated and the aqueous phase was extracted with CH2Cl2 (15 ml x3). The organic phases were pooled, washed with brine, dried over Na2SO4 and filtered. The solvent was removed under reduced pressure and the resulting crude product was purified by column chromatography with Hex:AcOEt.

Reference: [1]Location in patent: experimental part Zhang, Jinglei; Wang, Jie; Qiu, Zhuibai; Wang, Yang [Tetrahedron, 2011, vol. 67, # 36, p. 6859 - 6867]
[2]Location in patent: experimental part Patil, Rajendra D.; Joshi, Girdhar; Adimurthy, Subbarayappa; Ranu, Brindaban C. [Tetrahedron Letters, 2009, vol. 50, # 21, p. 2529 - 2532]
[3]Wu, Ping; Xu, Senhan; Xu, Hao; Hu, Haiyan; Zhang, Wei [Tetrahedron Letters, 2017, vol. 58, # 7, p. 618 - 621]
[4]Location in patent: experimental part Patil, Rajendra D.; Joshi, Girdhar; Adimurthy, Subbarayappa; Ranu, Brindaban C. [Tetrahedron Letters, 2009, vol. 50, # 21, p. 2529 - 2532]
[5]Location in patent: experimental part Patil, Rajendra D.; Joshi, Girdhar; Adimurthy, Subbarayappa; Ranu, Brindaban C. [Tetrahedron Letters, 2009, vol. 50, # 21, p. 2529 - 2532]
[6]Location in patent: experimental part Podgoršek, Ajda; Stavber, Stojan; Zupan, Marko; Iskra, Jernej [Tetrahedron, 2009, vol. 65, # 22, p. 4429 - 4439]
[7]Location in patent: experimental part Dai, Zhihong; Peng, Xinhua; Dong, Xiongzi; Shi, Chunjie; Rong, Yuan [Asian Journal of Chemistry, 2012, vol. 24, # 11, p. 4979 - 4985]
[8]Location in patent: experimental part Dai, Zhihong; Peng, Xinhua; Dong, Xiongzi; Shi, Chunjie; Rong, Yuan [Asian Journal of Chemistry, 2012, vol. 24, # 11, p. 4979 - 4985]
[9]Location in patent: experimental part Dai, Zhihong; Peng, Xinhua; Dong, Xiongzi; Shi, Chunjie; Rong, Yuan [Asian Journal of Chemistry, 2012, vol. 24, # 11, p. 4979 - 4985]
[10]Mendoza, Fabian; Ruíz-Guerrero, Rosario; Hernández-Fuentes, Carlos; Molina, Paulina; Norzagaray-Campos, Mariano; Reguera, Edilso [Tetrahedron Letters, 2016, vol. 57, # 50, p. 5644 - 5648]
  • 43
  • [ 100-42-5 ]
  • [ 38661-81-3 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 48 %Spectr. 2: 34 %Spectr. With hydrogen bromide; sodium nitrite In water; acetonitrile at 22℃; for 5h;
1: 91 %Spectr. 2: 7 %Spectr. With C22H24CuN4O3; oxygen; trifluoroacetic acid; lithium bromide In nitromethane at 60℃; for 20h; Inert atmosphere; 4.2.5 Catalytic bromination of styrene General procedure: A mixture of styrene (0.4mmol), LiBr (4.0mmol), CF3CO2H (1.2mmol) and Cu complex (5mol%) in CH3NO2 (1mL) was loaded in reaction tube and heated at 60°C under oxygen atmosphere for 20h. After the reaction, the yields were determined by 1H NMR integration with the use of methylsulfone as the internal standard in CDCl3.
1: 80 %Spectr. 2: 17 %Spectr. With C22H24CuN4O3; oxygen; trifluoroacetic acid; lithium bromide In toluene at 60℃; for 20h; Inert atmosphere; 4.2.5 Catalytic bromination of styrene General procedure: A mixture of styrene (0.4mmol), LiBr (4.0mmol), CF3CO2H (1.2mmol) and Cu complex (5mol%) in CH3NO2 (1mL) was loaded in reaction tube and heated at 60°C under oxygen atmosphere for 20h. After the reaction, the yields were determined by 1H NMR integration with the use of methylsulfone as the internal standard in CDCl3.
  • 44
  • [ 32353-49-4 ]
  • [ 93-52-7 ]
  • 1-ethyl-4-(2-phenylcyclopropyl)pyridinium bromide [ No CAS ]
YieldReaction ConditionsOperation in experiment
53% With 15-crown-5; potassium carbonate In acetonitrile at 65℃;
  • 45
  • 4-tert-butylbenzene sulfinic acid sodium salt [ No CAS ]
  • [ 93-52-7 ]
  • 1-tert-butyl-4-((E)-2-phenyl-ethenesulfonyl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
3% In N,N-dimethyl-formamide at 80℃; for 15h; 1-tert-Butyl-4-((E)-2-phenyl-ethenesulfonyl)-benzene (7c) A solution of 4-tert-butylbenzene sulfinic acid sodium salt (3.0 g, 13.6 mmol) and 1,2-dibromoethyl benzene (4.31 g, 16.3 mmol) in DMF (30 ml) was heated to 80 °C for 15h. The reaction mixture was purified by silica gel column chromatography (5%Ethyl acetate: hexane) to obtain 1-tert-Butyl-4-((E)-2-phenyl-ethenesulfonyl)-benzene (104 mg, 3%) as an off white solid, mp = 95 °C. LCMS (ESI): 301 (M+H); 1H-NMR (400MHz, CDCl3) δ 1.34 (s, 9H), 6.84-6.88 (d, J = 15.6 Hz, 1H), 7.38-7.49 (m, 5H), 7.54-7.57 (d, J = 8.4 Hz, 2H), 7.65-7.69 (d, J = 15.6 Hz, 1H), 7.85-7.88 (d, J = 8.4 Hz, 2H).
3% In N,N-dimethyl-formamide at 80℃; for 15h;
  • 46
  • [ 93-52-7 ]
  • [ 29847-04-9 ]
YieldReaction ConditionsOperation in experiment
80% With Caswell No. 744A In dimethyl sulfoxide at 25℃; for 13h; Inert atmosphere; Schlenk technique;
With Caswell No. 744A In dimethyl sulfoxide at 25℃; for 13.75h;
With Caswell No. 744A In dimethyl sulfoxide at 25℃; for 13.75h;
With Caswell No. 744A In dimethyl sulfoxide at 20℃; for 0.75h; 1 Example 1 50 mmol (5.2 g) of styrene was dissolved in 40 mL of carbon tetrachloride,A solution of bromine (8 g, 50 mmol) in carbon tetrachloride was added dropwise,Reaction at room temperature for two hours;After completion of the reaction, the solvent was evaporated to obtain an addition product.The resulting product was dissolved in dimethylsulfoxide (70 mL)Sodium azide (4.9 g, 75 mmol) was added;After 45 minutes of reaction, an aqueous solution of sodium hydroxide (2.0 g, 50 mmol) was added,After 1 hour of reaction, 100 mL of a saturated aqueous sodium hydrogencarbonate solution was added,Extracted with methylene chloride,The organic phase was dried over anhydrous sodium sulfate,Evaporation of the solvent gave the alkenyl azide compound.Finally, the alkenyl azide compound is dissolved in toluene,Reflux for four hours,At the end of this time, the solvent was evaporated and evaporated under reduced pressure to give the 2H-azapyridine compound.As shown in Figure 3,The reaction was carried out in a 10 mlschlenk reaction tube,After the reaction tube was evacuated and replaced with argon three times,10 mol% (4.9 mg) of cuprous acetate and 4 ml of solvent 1,4-dioxane were added,Stirring 5min;Then, 0.4 mmol (46.4 mg) of p-methylphenylacetylene 1a and 1.2 mmol (140.5 mg) of azaproenenidine 1b were added, and the reaction was stirred at room temperature for 12 hours.After completion of the reaction,After the solvent was removed using a rotary evaporator,The solid was dissolved in methylene chloride and subjected to silica gel column chromatography,With petroleum ether:Ethyl acetate = 20: 1-10: 1 eluent,To obtain 114.4 mg of a 3-alkynylpyrrole derivative 1c as a white solid,The isolated yield was 86%.Poly-substituted 3-alkynylpyrrole derivative 1c
With Caswell No. 744A In dimethyl sulfoxide at 20℃; for 13h; Inert atmosphere;
With Caswell No. 744A In dimethyl sulfoxide at 20℃; for 13.45h; Inert atmosphere;
With Caswell No. 744A In dimethyl sulfoxide at 25℃; for 13h; Inert atmosphere;

  • 47
  • [ 93-52-7 ]
  • [ 7654-06-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13.75 h / 25 °C 2: sodium hydroxide / lithium hydroxide monohydrate; dimethyl sulfoxide / 0.4 h / 25 °C / Inert atmosphere 3: toluene / 4 h / Reflux
Multi-step reaction with 2 steps 1: Caswell No. 744A / N,N-dimethyl-formamide / 20 °C / Inert atmosphere 2: toluene / Reflux; Inert atmosphere
Multi-step reaction with 2 steps 1.1: Caswell No. 744A / dimethyl sulfoxide / 14 h / 0 - 20 °C 1.2: 24 h / 20 °C 2.1: toluene / 2 h / Reflux
Multi-step reaction with 3 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13.75 h / 25 °C 2: sodium hydroxide / lithium hydroxide monohydrate / 24 h / 25 °C 3: toluene / 4 h
Multi-step reaction with 3 steps 1: Caswell No. 744A / dimethyl sulfoxide / 0.75 h / 20 °C 2: sodium hydroxide; lithium hydroxide monohydrate / 1 h / 20 °C 3: toluene / 4 h / Reflux
Multi-step reaction with 3 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13 h / 20 °C / Inert atmosphere 2: sodium hydroxide / 24 h / 20 °C 3: toluene / 4 h / Reflux
Multi-step reaction with 2 steps 1: Caswell No. 744A / N,N-dimethyl-formamide / 5 h 2: triethylamine / toluene / 0.67 h / 110 °C
Multi-step reaction with 2 steps 1: Caswell No. 744A / N,N-dimethyl-formamide / 20 °C 2: toluene / 2 h / 110 °C
Multi-step reaction with 3 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13.45 h / 20 °C / Inert atmosphere 2: sodium hydroxide / dimethyl sulfoxide; lithium hydroxide monohydrate / 24 h / 20 °C 3: toluene / 4 h / Reflux
Multi-step reaction with 2 steps 1: Caswell No. 744A / N,N-dimethyl-formamide 2: toluene / 0.5 h / Reflux
Multi-step reaction with 2 steps 1: Caswell No. 744A / N,N-dimethyl-formamide / 10 h / 20 °C 2: 1,4-diaza-bicyclo[2.2.2]octane / toluene / 2 h / 110 °C
Multi-step reaction with 2 steps 1: Caswell No. 744A / N,N-dimethyl-formamide / 100 °C / Inert atmosphere 2: triethylamine; toluene / 100 °C
Multi-step reaction with 3 steps 1: Caswell No. 744A / dimethyl sulfoxide / 13 h / 25 °C / Inert atmosphere 2: sodium hydroxide / lithium hydroxide monohydrate / 24 h / 25 °C 3: toluene / 4 h / Reflux

Reference: [1]Wang, Rui; Yu, Fabiao; Liu, Ping; Chen, Lingxin [Chemical Communications, 2012, vol. 48, # 43, p. 5310 - 5312]
[2]Loy, Nicole S. Y.; Kim, Sunggak; Park, Cheol-Min [Organic Letters, 2015, vol. 17, # 3, p. 395 - 397]
[3]Zhao, Yun-Zhou; Yang, Hai-Bin; Tang, Xiang-Ying; Shi, Min [Chemistry - A European Journal, 2015, vol. 21, # 9, p. 3562 - 3566]
[4]Chen, Lili; Li, Hongji; Li, Pinhua; Wang, Lei [Organic Letters, 2016, vol. 18, # 15, p. 3646 - 3649]
[5]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES; Dalian Institute of Chemical Physics (in: CAS) - CN105669513, 2016, A
[6]De, Aramita; Santra, Sougata; Hajra, Alakananda; Zyryanov, Grigory V.; Majee, Adinath [Journal of Organic Chemistry, 2019, vol. 84, # 18, p. 11735 - 11740]
[7]Zhou, Effie Y.; Knox, Hailey J.; Liu, Chang; Zhao, Weili; Chan, Jefferson [Journal of the American Chemical Society, 2019, vol. 141, # 44, p. 17601 - 17609]
[8]Jiang, Huanfeng; Nie, Biao; Ren, Qingyun; Wu, Wanqing; Zeng, Wei; Zhang, Ji; Zhang, Yingjun [Advanced synthesis and catalysis, 2020]
[9]De, Aramita; Majee, Adinath; Santra, Sougata; Zyryanov, Grigory V. [Organic Letters, 2020, vol. 22, # 10, p. 3926 - 3930]
[10]Shrestha, Pradeep; Dissanayake, Komadhie C.; Gehrmann, Elizabeth J.; Wijesooriya, Chamari S.; Mukhopadhyay, Atreyee; Smith, Emily A.; Winter, Arthur H. [Journal of the American Chemical Society, 2020, vol. 142, # 36, p. 15505 - 15512]
[11]Current Patent Assignee: FUDAN UNIVERSITY - CN112010880, 2020, A
[12]Yadav, Anuj K.; Tapia Hernandez, Rodrigo; Chan, Jefferson [Methods in Enzymology, 2021, vol. 657, p. 415 - 441]
[13]Balalaie, Saeed; Hosseinijei, Reyhaneh; Nikbakht, Ali; Rominger, Frank; Zahedian Tejeneki, Hossein [Organic and Biomolecular Chemistry, 2022, vol. 20, # 15, p. 3076 - 3080]
  • 48
  • [ 93-52-7 ]
  • [ 103-64-0 ]
YieldReaction ConditionsOperation in experiment
With potassium phosphate In ethanol at 80℃; for 0.166667h; Synthesis of acetylenes from vicinal dibromides General procedure: A mixture of vicinal dibromide (5 mmol), anhydrous K3PO4 (5 mmol), PEG-900 (1.25 mmol), and EtOH (10 mL) was stirred at 80 °C. The progress of the reaction was monitored by analysis of the samples using TLC and gas chromatography. When the vicinal dibromide had been completely converted into the monobromo product, a second portion of K3PO4 (5 mmol) was added.Following completion of the reaction the mixture was filtered and the filtrate was diluted with CH2Cl and washed several times with H2O. The organic phase was dried over MgSO4 and evaporated under vacuum to afford a mixture of product and the monobromo derivative. The acetylene was separated by vacuum distillation. The identity and purity of the products were confirmed by GC-MS and 1H NMR spectroscopy.
  • 49
  • [ 100-42-5 ]
  • [ 93-56-1 ]
  • [ 2425-28-7 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
With perchloric acid; C20H18N4O6S4V2*2Cs(1+)*2H2O; dihydrogen peroxide; potassium bromide In dichloromethane; water at 20℃; for 1h;
With perchloric acid; [MnIII(sal-aebmz-H)(sal-aebmz)]; water; dihydrogen peroxide; potassium bromide In dichloromethane at 20℃; for 1h;
With perchloric acid; dihydrogen peroxide; potassium bromide In dichloromethane; water at 40℃; for 1h; 2.5.1. Oxidative bromination of styrene General procedure: The catalyst (0.010 g), styrene (1.04 g, 10 mmol), KBr (2.38 g,20 mmol), aqueous 30% H2O2 (2.27 g, 20 mmol) and 70% aqueous HClO4 (5.72 g, 40 mmol, added in four equal portions at t = 0, 15,30 and 45 min) were stirred at 40 C in a two phase CH2Cl2-H2O (40 mL 50%, v/v mixture) system for 1 h. Every 15 min a small aliquot was withdrawn and after addition of 5 mL of CH2Cl2, it was washed with distilled water in a separating funnel and the organic layer was analyzed by gas chromatography. At the end of the reaction,the organic layer after processing as above, was evaporated and the residue was purified by column chromatography using 1% CH2Cl2 in n-hexane as an eluent. The products were identified by GC-MS and 1H NMR spectroscopy.
With perchloric acid; dihydrogen peroxide; potassium bromide In dichloromethane; water at 40℃; for 2h; Oxidative bromination of styrene Catalyst (0.015 g), styrene (1.04 g, 10 mmol), KBr (2.38 g, 20 mmol), aqueous 30% H2O2(2.27 g, 20 mmol) and 70% aqueous HClO4(2.86 g, 20 mmol, added in four equal portions at t = 0, 15, 30 and 45 min) were stirred at 40C in a biphasic dichloromethane-water (40 mL 50%, v/v mixture) system for 2 h. At every 15 min small aliquot of the reaction mixture present in organic layer was withdrawn and analyzed quantitatively by gas chromatography.
With perchloric acid; dihydrogen peroxide; potassium bromide In dichloromethane; water at 20℃; Oxidative bromination of styrene Warning HClO4 is potential oxidant, hence it must be handledcarefully: Complexes 4-6 were used as catalyst precursors to carryout the oxidative bromination of styrene. In a typical reaction, styrene(1.04 g, 10 mmol) was added to an aqueous solution (20 mL)of KBr (3.57 g, 30 mmol) in a 100 mL reaction flask, and then20 mL CH2Cl2 and 30% aqueous H2O2 (3.40 g, 30 mmol) wereadded. After adding 70% HClO4 (1.43 g, 10 mmol) and catalyst precursors(0.0010 g), the reaction mixture was stirred at room temperature.Three additional 10 mmol portions of 70% HClO4 werefurther added after every 15 min with continuous stirring. Theexperimental conditions (e.g. stirring speed, size of magnetic barand reaction flask) in all batches were kept as similar as possible.After 1 h the orange colored organic layer was separated using aseparatory funnel, washed with water and dried. The crude masswas re-dissolved in CH2Cl2 and insoluble material, if any, was removedby filtration. The solvent was evaporated and the reactionproducts were separated using a silica gel column. Elution of thecolumn with 1% CH2Cl2 in n-hexane first separated a mixture ofbromo derivatives, followed by 1-phenylethane-1,2-diol. The twobromo derivatives were finally separated from each other using anothersilica gel column and eluted with pure n-hexane. The productswere identified by GC-MS and 1H NMR spectra
With perchloric acid; C12H18MoN2O5; dihydrogen peroxide; potassium bromide In methanol; water at 24.84℃; for 0.5h;

  • 50
  • [ 536-74-3 ]
  • [ 93-52-7 ]
  • [ 1402355-13-8 ]
  • [ 1402355-14-9 ]
YieldReaction ConditionsOperation in experiment
With zinc In dichloromethane at 20℃; optical yield given as %de; stereoselective reaction;
74 % de With zinc In dichloromethane at 40℃; for 48h; Inert atmosphere; Schlenk technique; Overall yield = 52 %; Overall yield = 1.90 g; Procedure 1; E-Vinyl Bromides General procedure: In a Schlenk flask, the corresponding alkyne (1-20 mmol, 1.0 equiv) and bromoethylbenzene (1.2-1.5 equiv) were added via syringe and dissolved under an argon atmosphere in CH2Cl2 (1-20 mL). Zn powder (150 mol%) was added and if necessary the reaction temperature was controlled using an ice bath. The mixture was stirred for 2 h at r.t. and filtered over silica gel (pentane-Et2O,20:1). The solvent was removed and the residue was purified by column chromatography on silica gel (eluent as indicated) yielding the E-vinyl bromides 3, 6, 8, and 10.
  • 51
  • [ 100-42-5 ]
  • [ 70-11-1 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 83% 2: 6% With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione In 1,2-dimethoxyethane; water at 40℃; for 12h;
1: 91.7 %Chromat. 2: 6.8 %Chromat. With tetrabutyl-ammonium chloride; hydrogen bromide; dihydrogen peroxide In water at 90℃; for 11.5h;
  • 52
  • [ 100-42-5 ]
  • [ 124-38-9 ]
  • [ 4427-92-3 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 65% 2: 20% With N-Bromosuccinimide; 1,8-diazabicyclo[5.4.0]undec-7-ene In water for 3h;
  • 53
  • [ 100-42-5 ]
  • [ 1255944-34-3 ]
  • [ 7614-93-9 ]
  • 1,2-diphenyltricyclo[8.3.1.03,9]tetradec-3(9)-ene [ No CAS ]
  • [ 38661-81-3 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 60% 2: 44% 3: 42% 4: 4% With silica gel at 50℃; for 12h; 4.5 Acid-catalyzed reaction of 7-bromo-1-phenylcycloheptene (1a) with styrene Compound 1a (4g, 15.9mmol), styrene (1.66g, 15.9mmol), and 0.1g silica gel were stirred at 50°C for 12h. The crude material was purified by column chromatography (hexane) to give 2a (1.63g, 60%), 4 (0.17g, 4%), 5 (1.3g, 44%), 6 (0.7g, 42%). The spectral data for compounds 4, 5, and 6 are consistent with those reported in the literature.11-13 Compound 4: 1H NMR (300MHz, CDCl3) δ 7.41-7.36 (m, 5H), 5.15 (dd, 1H, J=5.6, 10.4Hz), 4.11-3.99 (m, 2H). Compound 5: 1H NMR (300MHz, CDCl3) δ 7.47-7.27 (m, 5H), 5.24 (q, 1H, J=6.9Hz), 2.07 (d, 3H, J=6.9Hz). Compound 6: 1H NMR (300MHz, CDCl3) δ 7.38-7.18 (m, 10H), 6.47-6.35 (m, 2H), 3.70-3.61 (m, 1H), 1.48 (d, 3H, J=7.0Hz).
  • 55
  • [ 93-52-7 ]
  • [ 91523-92-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1.1: potassium carbonate / methanol; tetrahydrofuran / 3 h / 20 °C 2.1: tert.-butyl lithium / diethyl ether; hexane / 0.5 h / -78 °C 2.2: -78 °C 3.1: hydrogenchloride / water / 2 h / 20 °C 4.1: copper diacetate; sodium sulfate; pyridine; oxygen / 1,2-dichloro-ethane / 48 h / 20 °C
Multi-step reaction with 3 steps 1.1: potassium carbonate / tetrahydrofuran; methanol / 3 h / 20 °C 2.1: tert.-butyl lithium / diethyl ether; pentane / 0.5 h / -78 °C / Inert atmosphere 2.2: -78 - 20 °C / Inert atmosphere 3.1: copper diacetate; sodium sulfate; pyridine / 1,2-dichloro-ethane / 24 h / 20 °C
Multi-step reaction with 3 steps 1.1: potassium carbonate / tetrahydrofuran; methanol / 3 h / 20 °C 2.1: tert.-butyl lithium / diethyl ether; pentane / 0.5 h / -78 °C / Inert atmosphere 2.2: -78 - 20 °C / Inert atmosphere 3.1: copper diacetate; sodium sulfate; pyridine / 1,2-dichloro-ethane / 48 h / 20 °C
Multi-step reaction with 3 steps 1.1: potassium carbonate / methanol; tetrahydrofuran / 3 h / 20 °C 2.1: tert.-butyl lithium / diethyl ether; pentane / -78 °C / Inert atmosphere 2.2: -78 - 20 °C / Inert atmosphere 2.3: 2 h / 20 °C / Inert atmosphere 3.1: copper diacetate; sodium sulfate; pyridine / 1,2-dichloro-ethane / 48 h / 20 °C
Multi-step reaction with 3 steps 1: potassium carbonate / methanol; tetrahydrofuran 2: tert.-butyl lithium / diethyl ether / -78 - 20 °C 3: pyridine; oxygen; copper(II) acetate monohydrate; sodium sulfate / 1,2-dichloro-ethane / 20 °C

  • 56
  • [ 100-42-5 ]
  • [ 55-21-0 ]
  • [ 93638-44-9 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 70% 2: 11% With N-Bromosuccinimide In chloroform at 40℃; for 3h;
1: 41% 2: 55% With N-Bromosuccinimide In chloroform at 40℃; for 8h;
  • 57
  • [ 6972-71-0 ]
  • [ 102921-26-6 ]
  • [ 71897-07-9 ]
YieldReaction ConditionsOperation in experiment
97.9% With N-hexylpyridine hexafluorophosphate; cisplatine; 4,7-Dimethyl-1,10-phenanthroline; diisopropanolamine; In toluene; at 120℃; for 8h;Inert atmosphere; In 400ml of toluene, 100mmol was added the compound of formula (II), a compound 200mmol of formula (III) (1,2- dibromo-ethylbenzene), 5mmol dichlorodiammine platinum,12mmol 4,7- dimethyl-1,10-phenanthroline, 300mmol 30mmol N- diisopropanolamine and hexyl pyridinium hexafluorophosphate, then purged twice with nitrogen, the reaction atmosphere such as a nitrogen atmosphere;The reaction system was raised from room temperature 120 , and the reaction was stirred at this temperature for 8 hours. After completion of the reaction, the reaction system was cooled to room temperature, and then saturated brine, separated with a camera, and the organic phase was concentrated in vacuo, the residue over 200 mesh silica gel column chromatography with petroleum ether and chloroform in a volume ratio of 4: 1 the mixture as an eluant, thereby obtaining the target compound of formula (I) 6,7- dimethyl-2-phenyl-quinoxaline, 97.9% yield.
  • 58
  • [ 100-42-5 ]
  • [ 13665-04-8 ]
  • [ 7402-45-1 ]
  • [ 70-11-1 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 71% 2: 7% 3: 13% 4: 6% With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione In 1,2-dimethoxyethane; water at 80℃; for 4h;
  • 59
  • [ 100-42-5 ]
  • [ 13665-04-8 ]
  • [ 70-11-1 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 73% 2: 11% 3: 6% With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione In 1,4-dioxane; water at 80℃; for 2h;
1: 69% 2: 20% 3: 7% With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione In 1,2-dimethoxyethane; water at 80℃; for 4h;
  • 60
  • [ 2227-79-4 ]
  • [ 93-52-7 ]
  • 2,5-diphenyl-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 61
  • [ 2362-62-1 ]
  • [ 93-52-7 ]
  • 5-phenyl-2-(p-tolyl)-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
67 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 62
  • [ 53515-19-8 ]
  • [ 93-52-7 ]
  • 5-phenyl-2-(o-tolyl)-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
83 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 63
  • [ 25984-63-8 ]
  • [ 102921-26-6 ]
  • 4-(5-phenyl-4,5-dihydrothiazol-2-yl)phenol [ No CAS ]
  • 64
  • [ 72505-21-6 ]
  • [ 102921-26-6 ]
  • C16H12F3NS [ No CAS ]
  • 5-phenyl-2-(4-(trifluoromethyl)phenyl)-4,5-dihydrothiazole [ No CAS ]
  • 65
  • [ 22179-72-2 ]
  • [ 93-52-7 ]
  • 2-(4-fluorophenyl)-5-phenyl-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
80 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 66
  • [ 93-52-7 ]
  • [ 175276-92-3 ]
  • 2-(2,4-difluorophenyl)-5-phenyl-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
80 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 67
  • [ 26197-93-3 ]
  • [ 93-52-7 ]
  • [ 1062214-33-8 ]
YieldReaction ConditionsOperation in experiment
102 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 68
  • [ 2521-24-6 ]
  • [ 93-52-7 ]
  • [ 1062214-31-6 ]
YieldReaction ConditionsOperation in experiment
85 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 69
  • [ 2227-62-5 ]
  • [ 93-52-7 ]
  • C15H12BrNS [ No CAS ]
  • 2-(3-bromophenyl)-5-phenyl-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
35% With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 70
  • [ 2362-64-3 ]
  • [ 93-52-7 ]
  • [ 1062214-21-4 ]
YieldReaction ConditionsOperation in experiment
70 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 71
  • [ 58952-14-0 ]
  • [ 93-52-7 ]
  • 2-(3,4-dimethoxyphenyl)-5-phenyl-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
72 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 72
  • [ 4714-67-4 ]
  • [ 93-52-7 ]
  • 4-(5-phenyl-4,5-dihydrothiazol-2-yl)aniline [ No CAS ]
YieldReaction ConditionsOperation in experiment
41 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 73
  • [ 4537-73-9 ]
  • [ 93-52-7 ]
  • 5-phenyl-2-(pyrimidin-2-yl)-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
38 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 74
  • [ 30216-44-5 ]
  • [ 93-52-7 ]
  • C15H12BrNS [ No CAS ]
  • 2-(2-bromophenyl)-5-phenyl-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
63% With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 75
  • [ 5346-38-3 ]
  • [ 102921-26-6 ]
  • 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrothiazole [ No CAS ]
  • 76
  • [ 4621-66-3 ]
  • [ 93-52-7 ]
  • [ 1062214-34-9 ]
YieldReaction ConditionsOperation in experiment
40 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 77
  • [ 2196-13-6 ]
  • [ 93-52-7 ]
  • 5-phenyl-2-(pyridin-4-yl)-4,5-dihydrothiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
21 mg With sodium hydrogencarbonate In acetonitrile at 80℃; for 15h;
  • 78
  • [ 13515-65-6 ]
  • [ 102921-26-6 ]
  • 2-isopropyl-5-phenyl-4,5-dihydrothiazole [ No CAS ]
  • 79
  • [ 100-42-5 ]
  • [ 96-09-3 ]
  • [ 2425-28-7 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
With perchloric acid; C17H15ClMoN2O5; dihydrogen peroxide; potassium bromide In water; acetonitrile at 24.84℃; 2.4. General procedure for catalytic bromoperoxidation reactions General procedure: cis-[MoO2(bzacLn)] or cis-[MoO2(acacLn)] (0.01 mmol), substrate (5 mmol), KBr (1.2 g, 10 mmol), H2O2 (1.05 ml of 30% w/w aqueous solution, 10 mmol) and HClO4 (1.1 ml of 60% aqueous solution, 10 mmol) were added to 6 ml of acetonitrile-water (1:1) mixed solvent in a 10 ml round bottom flask. The mixture was stirred for the desired time period at room temperature. After stirring it was diluted with 25 ml of water and then extracted with dichloromethane (2 x 7 ml). The dichloromethane extracts were combined ,dried over anhydrous sodium sulfate and then subjected to GC-MS analysis for identification of the products and calculation of the yields from the areas under the respective peaks.
With perchloric acid; C22H18MoN2O5; dihydrogen peroxide; potassium bromide In water; acetonitrile at 24.84℃; 2.4. General procedure for catalytic bromoperoxidation reactions General procedure: cis-[MoO2(bzacLn)] or cis-[MoO2(acacLn)] (0.01 mmol), substrate (5 mmol), KBr (1.2 g, 10 mmol), H2O2 (1.05 ml of 30% w/w aqueous solution, 10 mmol) and HClO4 (1.1 ml of 60% aqueous solution, 10 mmol) were added to 6 ml of acetonitrile-water (1:1) mixed solvent in a 10 ml round bottom flask. The mixture was stirred for the desired time period at room temperature. After stirring it was diluted with 25 ml of water and then extracted with dichloromethane (2 x 7 ml). The dichloromethane extracts were combined ,dried over anhydrous sodium sulfate and then subjected to GC-MS analysis for identification of the products and calculation of the yields from the areas under the respective peaks.
  • 80
  • [ 100-42-5 ]
  • bis(2-bromo-2-phenylethyl)selenide [ No CAS ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 12 %Spectr. 2: 75 %Spectr. With selenium dibromide In dichloromethane at -78℃; for 0.5h; Overall yield = 0.982 g; Bis(2-bromo-2-phenylethyl) selenide (4). A solution of 0.52 g (5 mmol) of vinylbenzene in 30 mL of methylene chloride was cooled to -78°C, and a solution of 2.5 mmol of SeBr2 in 40 mL of methylene chloride, cooled to -78°C, was added dropwise. The mixture was stirred for 30 min and allowed to warm up to room temperature with stirring (2 h). The mixture was filtered, washed with water, and dried over CaCl2, the solvent was distilled off on a rotary evaporator, and the residue was dried under reduced pressure. Yield of mixture 2/4 0.982 g (12% of 2 and 75% of 4, according to the 1H NMR data). We failed to isolate compound 4 by silica gel chromatography using hexane-carbon tetrachloride (1 : 6) as eluent. 1H NMR spectrum, δ, ppm: 3.44-3.54 m (4H, SeCH2), 4.59-4.63 m (2H, CHBr), 6.78-6.87 m (10H, Ph). 13C NMR spectrum, δC, ppm: 34.89 (SeCH2, JC-Se = 70 Hz), 50.72 (CHBr), 126.05 (Carom), 127.47 (Carom), 128.51 (Carom), 138.26 (Carom).
  • 81
  • [ 17356-08-0 ]
  • [ 93-52-7 ]
  • C10H14N4S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In ethanol for 5h; Reflux; 7 Preparation of thiourea salts: To install a temperature control device,A stirrer and a reflux condenser, as a reaction vessel,33.5 g (0.44 mol) of thiourea was weighed,Added to a four-necked flask,Then add 400 g of ethanol,Heating and stirring to completely dissolve thiourea,52.8 g (0.2 mol) of 1,2-dibromoethylbenzene was added dropwise,Reflux reaction conditions for 5 h,The mixture was stirred, cooled to room temperature, and the reaction solution was filtered off,And the solid was washed with ethanol, dried to constant weight,That is, phenyl diphenylene disulfide salt.
  • 82
  • [ 100-42-5 ]
  • [ 13323-81-4 ]
  • [ 38661-81-3 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 38 %Spectr. 2: 31 %Spectr. 3: 25 %Spectr. With sulfuric acid; C22H24CuN4O3; oxygen; lithium bromide In acetonitrile at 60℃; for 20h; Inert atmosphere; 4.2.5 Catalytic bromination of styrene General procedure: A mixture of styrene (0.4mmol), LiBr (4.0mmol), CF3CO2H (1.2mmol) and Cu complex (5mol%) in CH3NO2 (1mL) was loaded in reaction tube and heated at 60°C under oxygen atmosphere for 20h. After the reaction, the yields were determined by 1H NMR integration with the use of methylsulfone as the internal standard in CDCl3.
1: 42 %Spectr. 2: 26 %Spectr. 3: 24 %Spectr. With sulfuric acid; C22H24CuN4O3; oxygen; lithium bromide In acetonitrile at 60℃; for 20h; Inert atmosphere; 4.2.5 Catalytic bromination of styrene General procedure: A mixture of styrene (0.4mmol), LiBr (4.0mmol), CF3CO2H (1.2mmol) and Cu complex (5mol%) in CH3NO2 (1mL) was loaded in reaction tube and heated at 60°C under oxygen atmosphere for 20h. After the reaction, the yields were determined by 1H NMR integration with the use of methylsulfone as the internal standard in CDCl3.
  • 83
  • [ 100-42-5 ]
  • [ 13323-81-4 ]
  • [ 93-52-7 ]
YieldReaction ConditionsOperation in experiment
1: 83 %Spectr. 2: 15 %Spectr. With C22H24CuN4O3; oxygen; trifluoroacetic acid; lithium bromide In acetonitrile at 60℃; for 20h; Inert atmosphere; 4.2.5 Catalytic bromination of styrene General procedure: A mixture of styrene (0.4mmol), LiBr (4.0mmol), CF3CO2H (1.2mmol) and Cu complex (5mol%) in CH3NO2 (1mL) was loaded in reaction tube and heated at 60°C under oxygen atmosphere for 20h. After the reaction, the yields were determined by 1H NMR integration with the use of methylsulfone as the internal standard in CDCl3.
  • 84
  • [ 93-52-7 ]
  • [ 1612759-94-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: sodium azide 2: ammonium iodide / dimethyl sulfoxide; tetrahydrofuran / 1.5 h / 20 °C / Electrochemical reaction
Multi-step reaction with 2 steps 1: sodium azide / N,N-dimethyl-formamide / 20 °C 2: eosin Y disodium salt; nitrobenzene / ethanol / 14 h / 20 °C / Inert atmosphere; Irradiation
Multi-step reaction with 2 steps 1: sodium azide 2: ammonium iodide / dimethyl sulfoxide; tetrahydrofuran / 1.5 h / 20 °C / Electrolysis
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Chemical Structure| 57825-30-6

[ 57825-30-6 ]

1-(Bromomethyl)-4-ethylbenzene

Similarity: 0.81