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[ CAS No. 32779-37-6 ]

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2D
Chemical Structure| 32779-37-6
Chemical Structure| 32779-37-6
Structure of 32779-37-6 *Storage: {[proInfo.prStorage]}

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Product Details of [ 32779-37-6 ]

CAS No. :32779-37-6MDL No. :MFCD08275684
Formula : C4H2Br2N2 Boiling Point : 316.6°C at 760 mmHg
Linear Structure Formula :-InChI Key :-
M.W :237.88Pubchem ID :10955588
Synonyms :

Computed Properties of [ 32779-37-6 ]

TPSA : 25.8 H-Bond Acceptor Count : 2
XLogP3 : 1.9 H-Bond Donor Count : 0
SP3 : 0.00 Rotatable Bond Count : 0

Safety of [ 32779-37-6 ]

Signal Word:WarningClass:N/A
Precautionary Statements:P305+P351+P338UN#:N/A
Hazard Statements:H302-H319Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 32779-37-6 ]

  • Upstream synthesis route of [ 32779-37-6 ]
  • Downstream synthetic route of [ 32779-37-6 ]

[ 32779-37-6 ] Synthesis Path-Upstream   1~7

  • 1
  • [ 32779-37-6 ]
  • [ 98-80-6 ]
  • [ 38696-20-7 ]
  • [ 29134-16-5 ]
Reference: [1] Organic and Biomolecular Chemistry, 2003, vol. 1, # 17, p. 3069 - 3077
  • 2
  • [ 7752-82-1 ]
  • [ 32779-37-6 ]
YieldReaction ConditionsOperation in experiment
40% With tert.-butylnitrite; trimethylbenzylammonium bromide In 1,2-dibromomethane at 20℃; [00159] Scheme 1. Preparation of relevant pyri(mi)dyl halides A-H. Key: (a) NBS, NH4OAc, MeCN, rt, 5 min, pyr: 85-90percent; pym: quant; (b) pyr: RCHO, Na(CN)BH3, MeCN, reflux, 1-12h (82percent, R = C5Hn); pym: NaH, Rl, THF, rt, overnight (85percent, R = Me); (c) Me3(Bn)NBr, f-BuONO, CH2Br2, rt, overnight, pyr: 77-83percent; pym: 30- 40percent; (d) pym: HI, CH2CI2, 0°C, 80-85percent; (e) i. NaOH, Br2, H20, rt, 50-60percent, ii. POCI3, PhNEt2, reflux, 4h, 75-85percent, iii. HI, CH2CI2, 0°C, 80-85percent; (f) ROH, Na, rt, 1-12 h, quant.; (g) RZnl, CI2Pd(PPh3)2, DMF/THF, rt, overnight, pyr (Br): 72percent (R = C6H13), pym (I) 81 percent, (R = C6H13); (h) alkyne, Cul, CI2Pd(PPh3)2, Et3N, MeCN, rt, 1-12 h, quant. [00161] The pyrimidyl bromides were prepared in a similar manner, beginning with bromination of 2-aminopyrimidine. N-Alkylation could not be achieved by reductive amination (presumably due to the decreased nucleophilicity of the amine) and was instead accomplished using NaH and an appropriate alkyl halide to give (B). Nonaqueous diazotization/halo-dediazoniation was used to prepare 5-bromo-2- halopyrimidines, but in diminished yield relative to the analogous reaction with the 2- aminopyridine (again, presumably due to the decreased nucleophilicity of the amine group). Alternatively, 2-pyrimidinone could serve as a precursor to 5-bromo-2- halopyrimidines (Lutz, F.; Kawasaki, T.; Soai, K. Tetrahedron-Asymmetry 2006, 17, 486.) or as a substrate for alkylation to generate 5-bromo-2-alkoxypyrimidines (D) (Kokatla, H. P.; Lakshman, M. K. Org. Lett. 2010, 12, 4478.) Introduction of an alkyne substituent at the 2-position to give ( proceeded satisfactorily under Sonogoshira conditions, but alkylation using Negishi conditions was unselective. Since reduction of the 2- alkynylpyrimidyl bromide (F) to the corresponding 2-alkyl pyrimidyl bromide (H) was complicated by competing removal of the bromine, we turned to 5-bromo-2- iodopyrimidine as a precursor for the cross coupling reactions and saw a dramatic improvement in selectivity and yields.
Reference: [1] Journal of Organic Chemistry, 2012, vol. 77, # 16, p. 6908 - 6916
[2] Patent: WO2012/162818, 2012, A1, . Location in patent: Page/Page column 45-46
[3] Journal of Organic Chemistry, 2008, vol. 73, # 23, p. 9326 - 9333
  • 3
  • [ 38353-09-2 ]
  • [ 32779-37-6 ]
YieldReaction ConditionsOperation in experiment
60% With bromine; sodium hydroxide In water at 20℃; [00159] Scheme 1. Preparation of relevant pyri(mi)dyl halides A-H. Key: (a) NBS, NH4OAc, MeCN, rt, 5 min, pyr: 85-90percent; pym: quant; (b) pyr: RCHO, Na(CN)BH3, MeCN, reflux, 1-12h (82percent, R = C5Hn); pym: NaH, Rl, THF, rt, overnight (85percent, R = Me); (c) Me3(Bn)NBr, f-BuONO, CH2Br2, rt, overnight, pyr: 77-83percent; pym: 30- 40percent; (d) pym: HI, CH2CI2, 0°C, 80-85percent; (e) i. NaOH, Br2, H20, rt, 50-60percent, ii. POCI3, PhNEt2, reflux, 4h, 75-85percent, iii. HI, CH2CI2, 0°C, 80-85percent; (f) ROH, Na, rt, 1-12 h, quant.; (g) RZnl, CI2Pd(PPh3)2, DMF/THF, rt, overnight, pyr (Br): 72percent (R = C6H13), pym (I) 81 percent, (R = C6H13); (h) alkyne, Cul, CI2Pd(PPh3)2, Et3N, MeCN, rt, 1-12 h, quant. [00161] The pyrimidyl bromides were prepared in a similar manner, beginning with bromination of 2-aminopyrimidine. N-Alkylation could not be achieved by reductive amination (presumably due to the decreased nucleophilicity of the amine) and was instead accomplished using NaH and an appropriate alkyl halide to give (B). Nonaqueous diazotization/halo-dediazoniation was used to prepare 5-bromo-2- halopyrimidines, but in diminished yield relative to the analogous reaction with the 2- aminopyridine (again, presumably due to the decreased nucleophilicity of the amine group). Alternatively, 2-pyrimidinone could serve as a precursor to 5-bromo-2- halopyrimidines (Lutz, F.; Kawasaki, T.; Soai, K. Tetrahedron-Asymmetry 2006, 17, 486.) or as a substrate for alkylation to generate 5-bromo-2-alkoxypyrimidines (D) (Kokatla, H. P.; Lakshman, M. K. Org. Lett. 2010, 12, 4478.) Introduction of an alkyne substituent at the 2-position to give ( proceeded satisfactorily under Sonogoshira conditions, but alkylation using Negishi conditions was unselective. Since reduction of the 2- alkynylpyrimidyl bromide (F) to the corresponding 2-alkyl pyrimidyl bromide (H) was complicated by competing removal of the bromine, we turned to 5-bromo-2- iodopyrimidine as a precursor for the cross coupling reactions and saw a dramatic improvement in selectivity and yields.
Reference: [1] Patent: WO2012/162818, 2012, A1, . Location in patent: Page/Page column 45-46
  • 4
  • [ 32779-36-5 ]
  • [ 32779-37-6 ]
Reference: [1] Patent: US5371224, 1994, A,
[2] Patent: US5371224, 1994, A,
  • 5
  • [ 38353-06-9 ]
  • [ 32779-37-6 ]
YieldReaction ConditionsOperation in experiment
50% for 1.5 h; Heating / reflux A mixture of 5-bromo-lH-pyrimidin-2-one (see step (e) above; 1.40 g, 8.0 mmol), POBr3 (2.8 g, 9.8 mmol) and PBr3 (7.7 mL) was refluxed for 1.5 h. After cooling to room temperature the reaction was poured into a mixture of crushed ice and Na(at)C03 (saturated aq. solution) and extracted with EtOAc (3x100 mL). The combined organic extracts were washed with brine, dried with Na2S04 and concentrated. The residue was re-dissolved in EtOAc/light petrol (1: 1) and filtered through a silica pad. Concentration of the filtrate gave the sub-title compound (0.95 g, 50 percent).
Reference: [1] Patent: WO2005/123673, 2005, A1, . Location in patent: Page/Page column 84
  • 6
  • [ 38353-06-9 ]
  • [ 32779-37-6 ]
Reference: [1] Patent: WO2011/4276, 2011, A1, . Location in patent: Page/Page column 115
  • 7
  • [ 67-56-1 ]
  • [ 32779-37-6 ]
  • [ 14001-66-2 ]
Reference: [1] Journal of Organic Chemistry, 2008, vol. 73, # 23, p. 9326 - 9333
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