Structure of 608-21-9
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CAS No. : | 608-21-9 |
Formula : | C6H3Br3 |
M.W : | 314.80 |
SMILES Code : | BrC1=C(Br)C(Br)=CC=C1 |
MDL No. : | MFCD00192668 |
Boiling Point : | No data available |
InChI Key : | GMVJKSNPLYBFSO-UHFFFAOYSA-N |
Pubchem ID : | 11842 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With nitric acid; In 1,2-dichloro-ethane; at 0℃; for 1h; | In a 250-mL round-bottom flask was dissolved 5.00 g (15.9 mmol) of 23 in 100 mL of 1,2-dichloroethane and the mixture cooled to 0 C. To the vigorously stirred solution at 0 C was added 7.00 mL (159 mmol) of fuming HNO3 dropwise over 15 minutes. The mixture was stirred at 0 C for 1 h and then poured over 500 mL of ice. After 30 minutes, 100 mL of CH2Cl2 was added and the organic layers extracted with water (3 x 100 mL), saturated NaHCO3 (3 x 100 mL), brine (100 mL), and then dried over anhydrous magnesium sulfate. The contents were filtered and concentrated under reduced pressure. The crude material was recrystallized from hexanes to give 4.74 g (82%) of 2,3,4-tribromonitrobenzene 24 as an off-white solid: mp = 82-84 C. 1H NMR (CDCl3): d 7.76 (d, J = 8.6 Hz, 1H), 7.51 (d, J = 8.6 Hz, 1H); 13C NMR (CDCl3): d 132.6, 132.5, 131.1, 130.1, 123.7, 118.7; HRMS (EI) m/e calcd for C6H2Br3NO2 356.7635, found 356.7633. This compound has been reported in the literature, but no spectral or physical data except melting point was given: Chen, G.; Konstantinov, A. D.; Chittim, B. G.; Joyce, E. M.; Bols, N. C.; Bunce, N. J. Environ. Sci. Tech. 2001, 35, 3749-3756. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tert.-butylnitrite; copper(ll) bromide; In acetonitrile; at 60℃; for 1h; | In a 500-mL round-bottom flask was dissolved 5.78 g (25.9 mmol) of CuBr2 in 200 mL of dry CH3CN and the mixture heated to 60 C. To this warm solution was added 3.80 mL (31.9 mmol) tert-butyl nitrite, followed by a solution of 5.01 g (19.9 mmol) of commercially available 2,6-dibromoaniline 22 in 50 mL CH3CN. The mixture was stirred at 60 C for 1 h, then cooled to room temperature and poured into 200 mL 20% aqueous ammonia. The mixture was extracted with hexane (2 x 200 mL) and the combined organic phase was washed sequentially with 20% aqueous ammonia (100 mL), water (100 mL), brine (50 mL), and then dried over anhydrous magnesium sulfate. The contents were filtered and concentrated under reduced pressure. The resulting crude material was recrystallized from ethanol to give 5.12 g (80%) of 1,2,3-tribromobenzene 23 as an off-white solid, mp = 88-90 C. 1H NMR (CDCl3): d 7.58 (d, J = 8.0 Hz, 2 H), 7.03 (t, J = 8.0 Hz, 1H); 13C NMR (CDCl3): d 132.6, 129.2, 127.7, 126.2. The physical and spectral data is consistent with that which was previously reported for this compound: (1) Menzel, K.; Fisher, E. L.; DiMichele, L.; Frantz, D. E.; Nelson, T. D.; Kress, M. H. J. Org. Chem. 2006, 71, 2188-2191; (2) Teclechiel, D.; Sundstroem, M.; Marsh, G. Chemosphere 2009, 74, 421-427. The second reference includes low resolution mass spectral data. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; n-butyllithium; benzaldehyde; | Step 1: (3,5-dibromo-phenyl)-phenyl-methanol E3-A To a solution of 1,3,5-tribromobenzene (10 g, 0.0318 mole) in ether (500 g), under argon was added nBuLi in hexanes (13.4 mL, 0.0318 mole) dropwise at -78 C. During the intial cooling of the tribrombenzene in ether some solids crashed out of solution. After addition of nBuLi was complete the reaction was allowed to stir for 0.5 hours at which time neat benzaldehyde (3.55 mL, 0.035 mole) was added dropwise to the vigorously stirred reaction mixture. Once addition was complete the reaction was allowed to reach 0 C. and 100 mL of HCl was added to the mixture. This was extracted with ether two times, dried with brine and over sodium sulfate and concentrated to give an oil. The crude product was purified by chromatography with 5% EtOAc/Hexanes to afford E3-A as a colorless oil that solidified on the bench. Rf=0.44 (5%EtOAc/Hexanes) 1H NMR (400MHz, CDCl3) δ7.56-7.55 (m, 1H), 7.48-7.47 (m, 2H), 7.39-7.29 (m, 5H), 5.75 (d, 1H, j=3.48 Hz), 2.28-2.27 (d, 1H, j=3.48 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 2,3,5-trimethyl-pyridine; hexane; mineral oil; | PREPARATION 6 3-(3,5-Dibromophenoxy)pyridine Sodium hydride (3.24 g of a 60% dispersion in mineral oil) was added portionwise to a stirred mixture of 3-hydroxypyridine (15.4 g), 1,3,5-tribromobenzene (76.4 g), cuprous oxide (11.6 g) and collidine (400 ml). When evolution of hydrogen had ceased, the mixture was heated at 200 for 8 hours and then cooled. The cool mixture was diluted with ethyl acetate and water, basified with aqueous ammonia (SG 0.880) and then filtered. The filtered residue was washed with ethyl acetate, then the washings and organic phase of the filtrate combined, washed with saturated brine and dried (MgSO4). The ethyl acetate was evaporated under vacuum, the collidine removed by distillation under vacuum and the residue chromatographed on silica gel using ether:hexane (1:4) as eluent. The earlier fractions gave, after evaporation under vacuum, recovered tribromobenzene (42.5 g). The later fractions were evaporated under vacuum to afford the title compound as an oil (18.55 g); δ (CDCl3): 7.07(2H,s), 7.22-7.26(2H,m), 7.42 (1H,s), 8.42(1H,s), 8.47(1H,d). Found: C,40.49; H,2.17; N,4.19. C11 H7 Br2 NO requires C,40.16; H,2.14; N,4.26%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 5 Isomerization step: In accordance with the process of Example 1 under the condition shown in Table 3-1, bromine was added dropwise to a mixture of benzene and aluminum chloride to produce tribromobenzene and then, aluminum chloride was added and the mixture was heated to attain the isomerization. The reaction mixture was cooled and washed with water to obtain crude oily products shown in Table 3-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With n-butyllithium; In toluene; at -5 - 20℃; for 2.33333h;Product distribution / selectivity; | b) n-Butyllithium variant, from 1.2.3-tribromo-benzene; To a stirred solution of 1,2,3-tribromo-benzene (4.34g, 13.8 mmol) and 6,6-dimethylfulvene (2.38g, assay 92.6%, 20.7 mmol) in dry toluene (60 ml) under a nitrogen atmosphere, 5.5 ml of a 2.5M toluene solution of /j-butyllithium (14.5 mmol) were added dropwise at -5 to O0C within 10 minutes. After a further 10 minutes at O0C and 2 hours at ambient temperature, the reaction mixture was poured onto a saturated aqueous solution of ammonium chloride, extracted with ethyl acetate, washed with brine and water, dried over sodium sulphate and evaporated. Purification of the crude material on silca gel in hexane afforded 2.38g of the desired product as a yellow oil (assay 84% by g.l.c, 55% yield). |
With n-butyllithium; In toluene; at -5 - 20℃; for 2.33333h;Inert atmosphere; | To a stirred solution of 1 ,2,3-tribromo-benzene (4.34g, 13.8 mmol) and 6,6-dimethylfulvene (2.38 g, assay 92.6%, 20.7 mmol) in dry toluene (60 ml) under a nitrogen atmosphere, 5.5 ml of a 2.5M toluene solution of n-butyllithium (14.5 mmol) were added dropwise at -5 to 0C within 10 minutes. After a further 10 minutes at 0C and 2 hours at ambienttemperature, the reaction mixture was poured onto a saturated aqueous solution of ammonium chloride, extracted with ethyl acetate, washed with brine and water, dried over sodium sulphate and evaporated. Purification of the crude material on silca gel in hexane afforded 2.38 g of the desired product as a yellow oil (assay 84% by g.l.c, 55% yield). This reaction is also disclosed in WO 2007/068417. |
Tags: 608-21-9 synthesis path| 608-21-9 SDS| 608-21-9 COA| 608-21-9 purity| 608-21-9 application| 608-21-9 NMR| 608-21-9 COA| 608-21-9 structure
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