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[ CAS No. 86-90-8 ]

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2D
Chemical Structure| 86-90-8
Chemical Structure| 86-90-8
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Product Details of [ 86-90-8 ]

CAS No. :86-90-8MDL No. :MFCD00191323
Formula : C8H3BrO3 Boiling Point : 361.8°C at 760 mmHg
Linear Structure Formula :-InChI Key :N/A
M.W :227.01Pubchem ID :66590
Synonyms :

Computed Properties of [ 86-90-8 ]

TPSA : 43.4 H-Bond Acceptor Count : 3
XLogP3 : 2 H-Bond Donor Count : 0
SP3 : 0.00 Rotatable Bond Count : 0

Safety of [ 86-90-8 ]

Signal Word:WarningClass:N/A
Precautionary Statements:P261-P305+P351+P338UN#:N/A
Hazard Statements:H302-H315-H319-H335Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 86-90-8 ]

  • Upstream synthesis route of [ 86-90-8 ]
  • Downstream synthetic route of [ 86-90-8 ]

[ 86-90-8 ] Synthesis Path-Upstream   1~8

  • 1
  • [ 86-90-8 ]
  • [ 64169-34-2 ]
  • [ 19477-73-7 ]
YieldReaction ConditionsOperation in experiment
38% With sodium tetrahydroborate In 1,2-dimethoxyethane at 20 - 30℃; for 4 h; The feed solution for the reaction was prepared by dissolving 227 g of 4-bromophthalic anhydride in 300 g of ethylene glycol dimethyl ether at 20° C. This solution was then added to the reducing agent, which was prepared as a slurry of 22.7 g of sodium BOROHDYRIDE in 200 g ethylene glycol dimethyl ether at 20°C. As the starting material was added to the reducing agent slurry, an increase in temperature from 20°C to 30°C was noted. After approximately 3.0 hours, all of the 4-bromophthalic anhydride had been added to the sodium borohydride slurry, and the reaction was allowed to continue, with stirring, for a further one hour at 26° C. Neutralisation of the excess sodium borohydride was performed by the careful addition of 200 g water and 70 g hydrochloric acid (as a 32percent aqueous solution). The pH of the neutralized reaction mixture dropped to pH 1-2, and the temperature rose from 26° C to 31° C. Phase separation was achieved by heating the mixture to 50° C, at which point two clearly distinguishable phases were observed: a heavy aqueous phase and a clear organic phase. The lower, aqueous, phase (223 g) was carefully removed, following which the organic phase was washed with aqueous NaCl solution (200 g, 15percent w/w) to remove the residues of H3BO3 formed during the work-up, then the aqueous ethylene glycol dimethyl ether (262 g) was partially distilled off from the organic phase over a temperature range of 74 to 91° C in a reboiler. Crude 5-bromophthalide was then crystallized from the organic phase residue by controlled cooling of said residue from 91°C to 25° C over a period of one hour, following which the temperature was held constant at 25° C for a further one hour. The crystallized material was filtered and washed with aqueous 50percent ethylene glycol dimethyl ether. The filtration residue thus formed was found to contain approximately 80percent 5-bromophthalide and 20percent 6-bromophthalide. In order to further purify the desired product, a slurry of 240 g of the wet, crude 5-bromophthalide was prepared in 240 g of aqueous 90percent ethylene glycol dimethyl ether at 25° C. This slurry was then heated to 85° C to obtain a solution, and re-crystallisation of the 5-bromophthalide was achieved by lowering the temperature from 85° C to 25°C over a period of one hour, and then holding at the lower temperature for a further one hour. The crystallized product was then filtered and washed with 90 g of aqueous 90percent ethylene glycol dimethyl ether, following which 97 g of wet residue was dried at 80° C for a period of 2 hours. The dried product thus formed (83 g) was subjected to HPLC analysis, and was found to contain >99percent 5-bromophthalide. The direct yield was approximately 38percent.
33% With sodium tetrahydroborate In tetrahydrofuran at 5 - 25℃; for 3.5 h; The feed solution for the reaction was prepared by dissolving 197 g of 4-bromophthalic anhydride in 250 g of THF at 25° C. This solution (density = 1.15 g/ml) was then added to the reducing agent, which was prepared as a slurry of 18.5 g of sodium borohydride in 150 g THF pre-cooled to 5° C prior to the addition of said solution. As the starting material was added to the reducing agent slurry, an increase in temperature from 5°C to 15°C was noted. After approximately 2.5 hours, all of the 4-bromophthalic anhydride had been added to the sodium borohydride slurry, and the reaction was allowed to continue, with stirring, for a further one hour at 25° C. Neutralisation of the excess sodium borohydride was performed by the careful addition of 120 g water and 60g hydrochloric acid (as a 32percent aqueous solution). The pH of the neutralized reaction mixture dropped to pH 1-2, and the temperature rose from 25° C to 30° C. Phase separation was achieved by heating the mixture to 58° C, at which point two clearly distinguishable phases were observed: a heavy aqueous phase having a density of 1.15 G/ML, and a clear organic phase having a density of 1.03 g/ml. The lower, aqueous, phase (159 g) was carefully removed, following which the organic phase was washed with aqueous NaCl solution (140 g, 10percent w/w) to remove the residues of H3BO3 formed during the work-up, then the THF (267 g) was partially distilled off from the organic phase over a temperature range of 70 to 75° C in a reboiler. Crude 5-bromophthalide was then crystallized from the organic phase residue (317 g) by adding 30 g water and controlled cooling of said residue from 75° C to 30° C over a period of one hour, following which the temperature was held constant at 30° C for a further one hour. The crystallized material was filtered and washed with 100g THF. The filtration residue thus formed (113 g, LOD-25percent) was found to contain approximately 90percent 5-bromophthalide and 10percent 6-bromophthalide. In order to further purify the desired product, a slurry of 100 g of the wet, crude 5-bromophthalide was prepared in 140 g of THF containing 6percent water at 25° C. This slurry was then heated to 60° C, and held at that temperature for one hour. Re-crystallization of the 5-bromophthalide was achieved by lowering the temperature from 60° C to 25°C over a period of one hour, and then holding at the lower temperature for a further one hour. The crystallized product was then filtered and washed with 40 g of THF, following which 65 g of wet residue was dried at 80° C for a period of 2 hours. The dried product thus formed (53 g) was subjected to HPLC and NMR analysis, and was found to contain >98percent 5-bromophthalide. The direct yield was approximately 33percent. The filtrate contained approximately 21 g of a recoverable mixture of 5-bromophthalide (70percent) and 6- bromophthalide (30percent). The overall yield of this process (after recycling the mother liquor) was between 37 and 40percent.
Reference: [1] Patent: WO2004/89924, 2004, A1, . Location in patent: Page 7; 16-17
[2] Patent: WO2004/89924, 2004, A1, . Location in patent: Page 7; 14-15
[3] Patent: WO2004/89924, 2004, A1, . Location in patent: Page 19-20
[4] Patent: WO2004/89924, 2004, A1, . Location in patent: Page 19
[5] Patent: WO2005/73205, 2005, A1, . Location in patent: Page/Page column 29-30
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  • [ 28281-76-7 ]
Reference: [1] Journal of Natural Products, 2018, vol. 81, # 6, p. 1460 - 1467
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  • [ 82-73-5 ]
  • [ 36978-41-3 ]
YieldReaction ConditionsOperation in experiment
76.19% at 30℃; for 8 h; Inert atmosphere General procedure: In a 1000 ml three-necked flask, 18.3 g (0.1 mol) of 4-chlorophthalic anhydride and 18.3 g (0.1 mol) were added 3-chlorophthalic anhydride, 300 g of anisole as solvent, 0.13 g (0.001 mol) of nickel chloride as a catalyst, 0.198 g (0.001 mol) of C-1 as a catalyst ligand, and 0.03 g (0.0003 mol) of sodium bromide as a catalyst Auxiliary, 13 g (0.2 mol) of zinc powder was used as a reducing agent, and the reaction was stirred at 30 ° C for 8 hours under a nitrogen atmosphere. The reaction solution was filtered to remove insoluble solids in the reaction liquid. 300 g of methanol was added to the filtration mother liquor, and the product was precipitated, filtered, and dried to obtain 25.8 g of the product 2,3,3',4'-biphenyltetracarboxylic dianhydride, yield 87.7percent. The synthesis method was the same as in Example 1, except that the types of 4-substituted phthalic anhydride and 3-substituted phthalic anhydride were changed.
Reference: [1] Patent: CN108250169, 2018, A, . Location in patent: Paragraph 0010; 0055; 0065-0067
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  • [ 22803-05-0 ]
Reference: [1] Patent: US5081291, 1992, A,
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  • [ 19725-82-7 ]
Reference: [1] Justus Liebigs Annalen der Chemie, 1968, vol. 715, p. 159 - 163
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  • [ 171011-37-3 ]
YieldReaction ConditionsOperation in experiment
91%
Stage #1: With diisobutylaluminium hydride In toluene at 20℃; for 1.5 h; Cooling with ice
Stage #2: With hydrogenchloride In water; toluene at 0 - 20℃; for 1 h;
A 1 M solution of DIBAL-H in toluene (3 mL, 3 mM) was added to an ice-cooled solution of4-bromophthalic anhydride (106 mg, 0.47 mM) in anhyd. toluene (1 mL) and the whole was stirred atroom temperature (rt) for 1.5 h. After slow addition of 10percent HCl aq (0.7 mL) at 0 °C with stirringfollowed by dilution with toluene (1 mL) the mixture was stirred at rt for 1 h, filtered through Celite,and extracted with AcOEt (20 mL × 3). The organic solutions were washed with brine (10 mL), dried(MgSO4), and evaporated. Purification of the residue by column chromatography (SiO2, hexane : AcOEt= 1 : 1) gave 10 (89 mg, 91percent) as colorless solids, mp 67-67.5 °C.
63%
Stage #1: With lithium aluminium tetrahydride In tetrahydrofuran at 20℃; for 2 h;
Stage #2: With water In tetrahydrofuran; ethyl acetate
Lithium aluminum hydride (2.7 g, 70.5 mmol) was suspended in tetrahydrofuran anhydride (100 milliliter), and then a tetrahydrofuran anhydride solution (100 milliliter) of Compound 2 (8 g, 35.3 mmol) was dropped in the suspension at room temperature. After 2 hours stirring, ethylacetate (100 milliliter) and water (100 milliliter) were poured in the resultant reaction solution in this order. Subsequently, the resultant reaction solution was filtrated, and then an organic layer was separated by adding ethylacetate, followed by drying thereof with the use of magnesium sulfate anhydride. The solvent of the organic layer was distilled, and as a result, Compound 3 was obtained. Product Amount: 5.2 g, Yield: 63 percent
52% With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 10℃; for 2 h; A 250-mL round-bottom flask was charged with 5-bromo-1,3-dihydro-2-benzofuran- 1,3-dione (8.00 g, 35.2 mmol, 1.00 equiv) and THF (100 mL). Lithium aluminium hydride (2.69 g, 70.9 mmol, 2.00 equiv) was added at 0°C. The resulting solution was stirred for 2 h at 10 °C and quenched by EtOAc (50 mL). The resulting solution was diluted with water (100 mL). The pH value of the solution was adjusted to 3 with hydrochloric acid (1 mol/L). The resulting solution was extracted with EtOAc (2 x 100 mL) and the organic layers were combined, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was chromatographed on a silica gel column to provide 4.00 g (52percent yield) of(4-bromo-1,2- phenylene)dimethanol as a white solid. ‘H NMR (300 IVIFIz, Chloroform-cl) ö 7.66 - 7.70 (m, 1H), 7.43 - 7.47 (m, 1H), 7.23 (d, J= 7.8 Hz, 1H), 4.71 (s, 4H), 2.62 (br, 2H).
52% With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 10℃; for 2 h; Example 151: 1,1,1,3,3,3-Hexafluoropropan-2-yl 1-((1,3-dihydroisobenzofuran-5-yl)methyl)- 1,8-diazaspiro[4.5]decane-8-carboxylate Step 1: Synthesis of (4-bromo-1,2-phenylene)dimethano A flask was charged with 5-bromoisobenzofuran-1,3-dione (8.00 g, 35.2 mmol, 1.00 equiv), and THF (100 mL). LAH (2.69 g, 70.9 mmol, 2.00 equiv) was added at 0 C. The resulting solution was stirred for 2 h at 10 C and quenched with EtOAc (50 mL) and diluted with water (100 mL). The pH value of the solution was adjusted to 3 with 1 M HCl. The resulting solution was extracted with EtOAc (2 x 100 mL) and the organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The residue was chromatographed on a silica gel column with EtOAc/petroleum ether (1/2) to provide 4.00 g (52percent yield) of (4-bromo-1,2- phenylene)dimethanol as a white solid.1H NMR (300 MHz, Chloroform-d) ^ 7.66– 7.70 (m, 1H), 7.43– 7.47 (m, 1H), 7.23 (d, J = 7.8 Hz, 1H), 4.71 (s, 4H), 2.62 (br, 2H).

Reference: [1] Heterocycles, 2009, vol. 77, # 2, p. 991 - 1005
[2] Synlett, 2013, vol. 24, # 19, p. 2510 - 2514
[3] Research on Chemical Intermediates, 2013, vol. 39, # 1, p. 139 - 146
[4] Patent: EP1659129, 2006, A1, . Location in patent: Page/Page column 100
[5] Patent: WO2017/87854, 2017, A1, . Location in patent: Page/Page column 00315
[6] Patent: WO2017/197192, 2017, A1, . Location in patent: Paragraph 00377
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  • [ 536-74-3 ]
  • [ 119389-05-8 ]
Reference: [1] Patent: US2005/215820, 2005, A1, . Location in patent: Page/Page column 12
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  • [ 201940-08-1 ]
Reference: [1] Patent: WO2014/89324, 2014, A1,
[2] Patent: CN104016979, 2017, B,
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