Home Cart 0 Sign in  

[ CAS No. 77771-02-9 ] {[proInfo.proName]}

,{[proInfo.pro_purity]}
Cat. No.: {[proInfo.prAm]}
Chemical Structure| 77771-02-9
Chemical Structure| 77771-02-9
Structure of 77771-02-9 * Storage: {[proInfo.prStorage]}
Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Quality Control of [ 77771-02-9 ]

Related Doc. of [ 77771-02-9 ]

Alternatived Products of [ 77771-02-9 ]

Product Details of [ 77771-02-9 ]

CAS No. :77771-02-9 MDL No. :MFCD00042186
Formula : C7H4BrFO Boiling Point : -
Linear Structure Formula :- InChI Key :FAHZIKXYYRGSHF-UHFFFAOYSA-N
M.W :203.01 Pubchem ID :173604
Synonyms :

Calculated chemistry of [ 77771-02-9 ]

Physicochemical Properties

Num. heavy atoms : 10
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.0
Num. rotatable bonds : 1
Num. H-bond acceptors : 2.0
Num. H-bond donors : 0.0
Molar Refractivity : 39.49
TPSA : 17.07 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.91 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.7
Log Po/w (XLOGP3) : 2.29
Log Po/w (WLOGP) : 2.82
Log Po/w (MLOGP) : 2.63
Log Po/w (SILICOS-IT) : 3.08
Consensus Log Po/w : 2.5

Druglikeness

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

Water Solubility

Log S (ESOL) : -2.92
Solubility : 0.244 mg/ml ; 0.0012 mol/l
Class : Soluble
Log S (Ali) : -2.29
Solubility : 1.05 mg/ml ; 0.00518 mol/l
Class : Soluble
Log S (SILICOS-IT) : -3.48
Solubility : 0.0668 mg/ml ; 0.000329 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.4

Safety of [ 77771-02-9 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 77771-02-9 ]

* 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.

  • Upstream synthesis route of [ 77771-02-9 ]
  • Downstream synthetic route of [ 77771-02-9 ]

[ 77771-02-9 ] Synthesis Path-Upstream   1~22

  • 1
  • [ 77771-02-9 ]
  • [ 1007-16-5 ]
YieldReaction ConditionsOperation in experiment
91% With sodium chlorite In tetrahydrofuran; water at 50℃; for 5 h; Sodium chlorite (6.78 g, 75 mmol) and 4-fluoro-3-bromobenzaldehyde (24.63 mmol) were dissolved in 1: 1 THF/water (100 mL) and stirred vigorously at 50 oC for 5 h. EtOAc (250 mL) and IN HC1 (50 mL) was added and the layers were separated. The organic layer was washed with water (3 x 50 mL), then was extracted with 0. 5M NA2CO3 (10 x 50 mL). The combined basic aqueous layers were slowly acidified with concentrated HC1 while stirring, to precipitate the carboxylic acid product. The solid was collected via filtration and dried under high vacuum overnight (4.93 g, 91percent). A portion of the solid carboxylic acid was dissolved in chloroform (30 mL) and concentrated sulfuric acid was added. A reflux condenser was attached to the flask and the solution was heated to 55 oC. Sodium azide (2.36 g, 36.45 mmol) was added in 3 portions over 1 h. After 4 h, additional sulfuric acid (10 mL) and sodium azide (1 g) were added and the reaction was stirred at 55 oC for 16 h. The mixture was transferred to a large cooled flask and the sulfuric acid was slowly quenched with 5N sodium hydroxide. The solution was adjusted to PH-8 and the aqueous solution was extracted with DCM (5 x 30 mL). The organic extracts were dried over sodium sulfate and concentrated in vacuo to yield a dark brown oil (2.2 g, 95percent) that solidified upon standing. 1H-NMR (CDC13): δ 6.94 (t, 8.4 Hz), 6.88 (dd, 1H, J = 2.8, 5.6 Hz), 6.58 (m, 1H), 3.62 (s, 2H).
56%
Stage #1: With potassium permanganate In water for 4 h; Heating / reflux
Stage #2: With hydrogenchloride In water
3-Bromo-4-fluoro-benzaldehyde (10.0 g, 49 mmol) in [H20] (150 mL, followed by the addition [OF KMNO4] (15.5 g, [98] mmol) heated at reflux (foams extensively) for 1 h, then added additional [KMN04] (15.5 g, 98 mmol) and continued heating for another 3 h. The reaction was cooled to rt, then filtered through Celite. The solution was acidified with HC1, and the resulting white precipitate was filtered off, to afford 6.1 g (56percent) of a white solid.
Reference: [1] Tetrahedron Letters, 2007, vol. 48, # 50, p. 8918 - 8921
[2] Patent: WO2003/99805, 2003, A1, . Location in patent: Page 434
[3] Journal of Fluorine Chemistry, 2000, vol. 105, # 1, p. 107 - 109
[4] Patent: WO2004/18414, 2004, A2, . Location in patent: Page 57
[5] Patent: WO2004/18414, 2004, A2, . Location in patent: Page 75-76
  • 2
  • [ 7758-19-2 ]
  • [ 77771-02-9 ]
  • [ 656-64-4 ]
YieldReaction ConditionsOperation in experiment
95% With hydrogenchloride; sodium hydroxide; sulfuric acid In tetrahydrofuran; chloroform; water; ethyl acetate a
3-Bromo-4-fluoro-phenylamine
Sodium chlorite (6.78 g, 75 mmol) and 4-fluoro-3-bromobenzaldehyde (24.63 mmol) were dissolved in 1:1 THF/water (100 mL) and stirred vigorously at 50° C. for 5 h. EtOAc (250 mL) and 1N HCl (50 mL) was added and the layers were separated.
The organic layer was washed with water (3*50 mL), then was extracted with 0.5M Na2CO3 (10*50 mL).
The combined basic aqueous layers were slowly acidified with concentrated HCl while stirring, to precipitate the carboxylic acid product.
The solid was collected via filtration and dried under high vacuum overnight (4.93 g, 91percent).
A portion of the solid carboxylic acid was dissolved in chloroform (30 mL) and concentrated sulfuric acid was added.
A reflux condenser was attached to the flask and the solution was heated to 55° C. Sodium azide (2.36 g, 36.45 mmol) was added in 3 portions over 1 h.
After 4 h, additional sulfuric acid (10 mL) and sodium azide (1 g) were added and the reaction was stirred at 55° C. for 16 h.
The mixture was transferred to a large cooled flask and the sulfuric acid was slowly quenched with 5N sodium hydroxide.
The solution was adjusted to pH~8 and the aqueous solution was extracted with DCM (5*30 mL).
The organic extracts were dried over sodium sulfate and concentrated in vacuo to yield a dark brown oil (2.2 g, 95percent) that solidified upon standing. 1H-NMR (CDCl3): δ 6.94 (t, 8.4 Hz), 6.88 (dd, 1H, J=2.8, 5.6 Hz), 6.58 (m, 1H), 3.62 (s, 2H).
Reference: [1] Patent: US2004/9995, 2004, A1,
  • 3
  • [ 77771-02-9 ]
  • [ 399-00-8 ]
Reference: [1] Organic Letters, 2017, vol. 19, # 23, p. 6280 - 6283
  • 4
  • [ 13061-96-6 ]
  • [ 77771-02-9 ]
  • [ 135427-08-6 ]
Reference: [1] Journal of Medicinal Chemistry, 2001, vol. 44, # 20, p. 3302 - 3310
  • 5
  • [ 459-57-4 ]
  • [ 77771-02-9 ]
YieldReaction ConditionsOperation in experiment
97% at 30 - 40℃; for 5.91667 h; Inert atmosphere Into a 500 mL four necked flask fitted with an overhead stirrer, a condenser and a thermometer pocket, 65percent Oleum 204g (7.5 times w.r.t. 4- Fluorobenzaldehyde ) was added to the flask slowly followed by iodine 0.27g (1 wtpercent w.r.t 4-Fluorobenzaldehyde) addition. The mixture was stirred under N2 atm. for 5 min. Then zinc bromide 0.68g (2.5wtpercent w.r.t 4- Fluorobenzaldehyde) was added to the reaction mass and the stirring was continued for another 5.0min. Then 4-Fluorobenzaldehyde (27.2g, 0.219mole) was added dropwise over a period of 1.0 h at temperature below 300C. The resulting mixture was stirred for 15 min and then bromine (6.8mL, 0.13 lmol) was added drop wise over a period of 3h at a temperature below 300C. Then the reaction mass was heated to 400C and maintained at same temperature for 90 min. and the reaction was monitored by G.C every 30 min. G.C areapercent showed 98percent product formation. The reaction mass was cooled to 10 0C and was quenched in ice (128.Og) over a period of 2h at a temperature below 25 0C. The organic portion was extracted with 2x 100 mL of toluene followed by washing with 3xl00mL water. The organic layer was treated with thiosulfate to remove unreacted bromine present in the crude. The final mass was washed with water and then the organic layer was separated and dried over Na2SO4 and the liquid was evaporated to give crude pale yellow product 43.19 gm ( 97percent yield). GC purity was 96percent.
Reference: [1] Patent: WO2010/86877, 2010, A2, . Location in patent: Page/Page column 11-12
[2] Patent: US5225607, 1993, A,
[3] Patent: US4791139, 1988, A,
[4] Patent: US4792563, 1988, A,
[5] Patent: EP240121, 1991, B1,
  • 6
  • [ 77771-03-0 ]
  • [ 77771-02-9 ]
Reference: [1] Synthetic Communications, 2009, vol. 39, # 2, p. 366 - 370
[2] Patent: US4626601, 1986, A,
[3] Patent: US4626601, 1986, A,
[4] Patent: US4626601, 1986, A,
  • 7
  • [ 2973-78-6 ]
  • [ 77771-02-9 ]
Reference: [1] Organic Letters, 2015, vol. 17, # 3, p. 544 - 547
  • 8
  • [ 459-57-4 ]
  • [ 107-06-2 ]
  • [ 77771-02-9 ]
Reference: [1] Patent: US4626601, 1986, A,
  • 9
  • [ 701914-09-2 ]
  • [ 77771-02-9 ]
Reference: [1] Journal of Organic Chemistry, 2018, vol. 83, # 15, p. 7852 - 7859
  • 10
  • [ 77771-02-9 ]
  • [ 180302-35-6 ]
Reference: [1] Organic Preparations and Procedures International, 2000, vol. 32, # 1, p. 88 - 91
  • 11
  • [ 77771-02-9 ]
  • [ 171050-06-9 ]
Reference: [1] Patent: WO2011/71570, 2011, A1,
  • 12
  • [ 77771-02-9 ]
  • [ 709-45-5 ]
Reference: [1] Patent: WO2016/16316, 2016, A1,
  • 13
  • [ 77771-02-9 ]
  • [ 79630-23-2 ]
YieldReaction ConditionsOperation in experiment
97.5% With ammonium hydroxide; iodine In tetrahydrofuran at 5 - 20℃; Tetrahydrofuran (100 ml) was added to a 250 ml reaction flask. 3-Bromo-4-fluorobenzaldehyde (10 g, 49.2 mmol) and aqueous ammonia (40 ml) were added with stirring. add elemental iodine (25 g, 98.5 mmol) in portions by cooling to 5 °C. Then, the reaction is raised to ambient temperature for 2 to 3 hours, and the reaction is completed. The reaction solution was poured into an aqueous solution of 10percent sodium sulfite (200 g), and extracted twice with methyl t-butyl ether (100 ml).Dry over anhydrous sodium sulfate, concentrate under reduced pressure, remove solvent, add n-heptane (20 ml), and then cool to 0-10 °C for 1h. Filtration and drying under reduced pressure gave 3-bromo-4-fluorobenzonitrile (9.6 g, yield: 97.5percent). The NMR spectrum of this compound was determined to be the same as the product of Example 1.
Reference: [1] Patent: CN108623496, 2018, A, . Location in patent: Page/Page column 0043-0048
  • 14
  • [ 77771-02-9 ]
  • [ 218301-22-5 ]
YieldReaction ConditionsOperation in experiment
100%
Stage #1: at 170℃; for 24 h;
Stage #2: With celite In 1-methyl-pyrrolidin-2-one at 80℃; for 1 h;
Preparation of 2-fluoro-5-formylbenzonitrileTo NMP (40ml) were added 3-bromo-4-fluorobenzaldehyde (lOg, 0.05mol) and CuCN (5g, 0.055mol). The resulting mixture was heated at 170°C for 24h until the reaction finished (monitored by TLC), and cooled to 80 °C, lOg of celite was added and stirred for lh at this temperature. The reaction mixture then was cooled to room temperature, and partitioned between ethyl acetate(250ml) and water( 125ml), the organic phase was washed with water and brine, dried, filtered, and concentrated to give the crude. Then the crude was purified by column chromatography on silica gel (Petroleum ether : Ethyl Acetate=4: l) to afford target compound (8g, 100percent) as a light yellow solid.]HNMR (CDCI3): δ 9.99 (1H, S), 8.18 (2H, m), 7.43(1H, m).
100% at 170℃; for 24 h; Preparation of 2-fluoro-5-formylbenzonitrile
To NMP (40 ml) were added 3-bromo-4-fluorobenzaldehyde (10 g, 0.05 mol) and CuCN (5 g, 0.055 mol).
The resulting mixture was heated at 170 for 24 h until the reaction finished (monitored by TLC), and cooled to 80, 10 g of celite was added and stirred for 1 h at this temperature.
The reaction mixture then was cooled to room temperature, and partitioned between ethyl acetate (250 ml) and water (125 ml), the organic phase was washed with water and brine, dried, filtered, and concentrated to give the crude.
Then the crude was purified by column chromatography on silica gel (Petroleum ether:Ethyl Acetate=4:1) to afford target compound (8 g, 100percent) as a light yellow solid.
1HNMR (CDCl3): δ 9.99 (1H, S), 8.18 (2H, m), 7.43 (1H, m).
Reference: [1] Patent: WO2012/71684, 2012, A1, . Location in patent: Page/Page column 22
[2] Patent: US2013/224107, 2013, A1, . Location in patent: Paragraph 0137; 0138
[3] Journal of Physical Chemistry B, 2010, vol. 114, # 45, p. 14157 - 14167
[4] Patent: WO2011/71570, 2011, A1, . Location in patent: Page/Page column 176-177
  • 15
  • [ 544-92-3 ]
  • [ 77771-02-9 ]
  • [ 218301-22-5 ]
Reference: [1] Organic Preparations and Procedures International, 2000, vol. 32, # 1, p. 88 - 91
  • 16
  • [ 77771-02-9 ]
  • [ 763114-26-7 ]
Reference: [1] Patent: WO2012/71684, 2012, A1,
[2] Patent: US2013/224107, 2013, A1,
  • 17
  • [ 77771-02-9 ]
  • [ 473416-91-0 ]
Reference: [1] Journal of the American Chemical Society, 2018, vol. 140, # 8, p. 2789 - 2792
  • 18
  • [ 2033-24-1 ]
  • [ 77771-02-9 ]
  • [ 866862-24-0 ]
Reference: [1] Patent: WO2014/74422, 2014, A1, . Location in patent: Paragraph 00180
  • 19
  • [ 77771-02-9 ]
  • [ 763114-25-6 ]
Reference: [1] Patent: WO2012/71684, 2012, A1,
[2] Patent: US2013/224107, 2013, A1,
  • 20
  • [ 77771-02-9 ]
  • [ 1021298-68-9 ]
Reference: [1] Patent: US2013/224107, 2013, A1,
  • 21
  • [ 77771-02-9 ]
  • [ 501420-63-9 ]
Reference: [1] Patent: WO2011/71565, 2011, A1,
[2] Patent: WO2010/93845, 2010, A1,
  • 22
  • [ 77771-02-9 ]
  • [ 866862-25-1 ]
Reference: [1] Patent: WO2014/74422, 2014, A1,
Same Skeleton Products
Historical Records

Related Functional Groups of
[ 77771-02-9 ]

Fluorinated Building Blocks

Chemical Structure| 1143502-70-8

[ 1143502-70-8 ]

3-Bromo-4,5-difluorobenzaldehyde

Similarity: 0.94

Chemical Structure| 188813-02-7

[ 188813-02-7 ]

3-Bromo-5-fluorobenzaldehyde

Similarity: 0.94

Chemical Structure| 1007-15-4

[ 1007-15-4 ]

3'-Bromo-4'-fluoroacetophenone

Similarity: 0.90

Chemical Structure| 357405-75-5

[ 357405-75-5 ]

4-Bromo-2,5-difluorobenzaldehyde

Similarity: 0.90

Chemical Structure| 135564-22-6

[ 135564-22-6 ]

4-Bromo-3,5-difluorobenzaldehyde

Similarity: 0.88

Aryls

Chemical Structure| 1143502-70-8

[ 1143502-70-8 ]

3-Bromo-4,5-difluorobenzaldehyde

Similarity: 0.94

Chemical Structure| 188813-02-7

[ 188813-02-7 ]

3-Bromo-5-fluorobenzaldehyde

Similarity: 0.94

Chemical Structure| 1007-15-4

[ 1007-15-4 ]

3'-Bromo-4'-fluoroacetophenone

Similarity: 0.90

Chemical Structure| 357405-75-5

[ 357405-75-5 ]

4-Bromo-2,5-difluorobenzaldehyde

Similarity: 0.90

Chemical Structure| 135564-22-6

[ 135564-22-6 ]

4-Bromo-3,5-difluorobenzaldehyde

Similarity: 0.88

Bromides

Chemical Structure| 1143502-70-8

[ 1143502-70-8 ]

3-Bromo-4,5-difluorobenzaldehyde

Similarity: 0.94

Chemical Structure| 188813-02-7

[ 188813-02-7 ]

3-Bromo-5-fluorobenzaldehyde

Similarity: 0.94

Chemical Structure| 1007-15-4

[ 1007-15-4 ]

3'-Bromo-4'-fluoroacetophenone

Similarity: 0.90

Chemical Structure| 357405-75-5

[ 357405-75-5 ]

4-Bromo-2,5-difluorobenzaldehyde

Similarity: 0.90

Chemical Structure| 135564-22-6

[ 135564-22-6 ]

4-Bromo-3,5-difluorobenzaldehyde

Similarity: 0.88

Aldehydes

Chemical Structure| 1143502-70-8

[ 1143502-70-8 ]

3-Bromo-4,5-difluorobenzaldehyde

Similarity: 0.94

Chemical Structure| 188813-02-7

[ 188813-02-7 ]

3-Bromo-5-fluorobenzaldehyde

Similarity: 0.94

Chemical Structure| 357405-75-5

[ 357405-75-5 ]

4-Bromo-2,5-difluorobenzaldehyde

Similarity: 0.90

Chemical Structure| 135564-22-6

[ 135564-22-6 ]

4-Bromo-3,5-difluorobenzaldehyde

Similarity: 0.88

Chemical Structure| 57848-46-1

[ 57848-46-1 ]

4-Bromo-2-fluorobenzaldehyde

Similarity: 0.88