[ CAS No. 32779-37-6 ] {[proInfo.proName]}

Name: 32779-37-6|2,5-Dibromopyrimidine|98%
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Quality Control of [ 32779-37-6 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 32779-37-6 ]

Product Details of [ 32779-37-6 ]

CAS No. :	32779-37-6	MDL No. :	MFCD08275684
Formula :	C₄H₂Br₂N₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	XAHITOJPIWZJHD-UHFFFAOYSA-N
M.W :	237.88	Pubchem ID :	10955588
Synonyms :

Calculated chemistry of [ 32779-37-6 ]

Physicochemical Properties

Num. heavy atoms :	8
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	0
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	37.43
TPSA :	25.78 Å²

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) :	-6.39 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.95
Log Po/w (XLOGP3) :	1.92
Log Po/w (WLOGP) :	2.0
Log Po/w (MLOGP) :	1.16
Log Po/w (SILICOS-IT) :	2.42
Consensus Log Po/w :	1.89

Druglikeness

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

Water Solubility

Log S (ESOL) :	-3.08
Solubility :	0.198 mg/ml ; 0.000833 mol/l
Class :	Soluble
Log S (Ali) :	-2.08
Solubility :	1.96 mg/ml ; 0.00822 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-3.36
Solubility :	0.103 mg/ml ; 0.000434 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.76

Safety of [ 32779-37-6 ]

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

Application In Synthesis of [ 32779-37-6 ]

* 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 [ 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 ]

Yield	Reaction Conditions	Operation 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 ]

Yield	Reaction Conditions	Operation 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 ]

Yield	Reaction Conditions	Operation 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

[ 32779-37-6 ] Synthesis Path-Downstream 1~61

2
[ 115-19-5 ]
[ 32779-37-6 ]
[ 423922-92-3 ]

Reference： [1]Journal of Materials Chemistry,2002,vol. 12,p. 173 - 180

3
[ 32779-37-6 ]
[ 203927-98-4 ]
[ 634589-28-9 ]

Reference： [1]Organic and Biomolecular Chemistry,2003,vol. 1,p. 3069 - 3077

4
[ 32779-37-6 ]
[ 98-80-6 ]
[ 38696-20-7 ]
[ 29134-16-5 ]

Reference： [1]Organic and Biomolecular Chemistry,2003,vol. 1,p. 3069 - 3077

5
[ 32779-37-6 ]
[ 98-80-6 ]
[ 29134-16-5 ]

Reference： [1]Organic and Biomolecular Chemistry,2003,vol. 1,p. 3069 - 3077

6
trans-4-methylaminomethyl-cyclohexanecarboxylic acid hydrochloride [ No CAS ]
[ 32779-37-6 ]
trans-4-[(5-bromo-pyrimidin-2-yl)-methyl-amino]-methyl}-cyclohexanecarboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With N-ethyl-N,N-diisopropylamine; In ISOPROPYLAMIDE; at 120℃; for 1h;	7.1 A mixture of 0.42 g (2.0 mmol) of trans-4-methylaminomethyl-cyclohexanecarboxylic acid-HCl, 1.85 mL (1.1 mmol) of Huenig's base and 0.57 g (2.4 mmol) of <strong>[32779-37-6]2,5-dibromo-pyrimidine</strong> [Brown and Arantz, J. Chem. Soc. C Issue 10, 1889-1891 (1971)] in 2 mL of DMA was placed in the microwave and heated to 120 C. for 1 h. The solvent was evaporated, partitioned between Et2O (*3)/aqueous 10% KH2PO4, dried over Na2SO4 and evaporated to yield 0.604 g (92%) of trans-4-[(5-bromo-pyrimidin-2-yl)-methyl-amino]-methyl}-cyclohexanecarboxylic acid, MS: 326 (M-H-, 1Br), MP: 172-174 C.

Reference： [1]Patent: US2005/65210,2005,A1 .Location in patent: Page/Page column 20

7
[ 38353-06-9 ]
[ 32779-37-6 ]

Yield	Reaction Conditions	Operation in experiment
50%	With phosphorus tribromide; phosphorus(V) oxybromide; for 1.5h;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 %).

Reference： [1]Patent: WO2005/123673,2005,A1 .Location in patent: Page/Page column 84

8
trans-3-(4-Methylamino-cyclohexyl)-prop-2-yn-1-ol [ No CAS ]
[ 32779-37-6 ]
trans-3-{4-[(5-Bromo-pyrimidin-2-yl)-methyl-amino]-cyclohexyl}-prop-2-yn-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
0.72 g (73%)	With N-ethyl-N,N-diisopropylamine;	1.7 A mixture of 0.51 g (3.05 mmol) trans-3-(4-Methylamino-cyclohexyl)-prop-2-yn-1-ol, 0.87 g (3.66 mmol) <strong>[32779-37-6]2,5-dibromo-pyrimidine</strong> [Brown, Desmond J.; Arantz, B. W., Pyrimidine reactions. XXII. Relative reactivities of corresponding chloro-, bromo-, and iodopyrimidines in aminolysis. J. Chem. Soc. C (1971), Issue 10, 1889-91] and 1.78 ml (10.34 mmol) N-ethyldiisopropylamine was heated for 2.5 h at 80 C. The reaction was cooled, evaporated and partitioned between aqueous saturated NaHCO3/Et2O (3*). The organic phases were washed with aqueous 10% NaCl, dried (NaSO4) and evaporated. Flash chromatography on silica gel (hexane/EtOAc 95:5) gave 0.72 g (73%) of trans-3-{4-[(5-Bromo-pyrimidin-2-yl)-methyl-amino]-cyclohexyl}-prop-2-yn-1-ol, mp: 156-157 C.; MS: 324 (MH+, 1Br).

Reference： [1]Patent: US2003/186984,2003,A1

9
[ 1378812-15-7 ]
[ 32779-37-6 ]
trans-4-{4-[(5-Bromo-pyrimidin-2-yl)-methyl-amino]-cyclohexyl}-but-3-yn-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1.37 g (69%)	With N-ethyl-N,N-diisopropylamine;	5.4 A mixture of 1.06 g (5.85 mmol) trans-4-(4-Methylamino-cyclohexyl)-but-3-yn-1-ol, 1.67 g (7.02 mmol) of <strong>[32779-37-6]2,5-dibromo-pyrimidine</strong> [Brown, Desmond J.; Arantz, B. W., Pyrimidine reactions. XXII. Relative reactivities of corresponding chloro-, bromo-, and iodopyrimidines in aminolysis. J. Chem. Soc. C (1971), Issue 10, 1889-91] and 3.38 ml (19.88 mmol) N-ethyldiisopropylamine were heated for 2 h at 85 C., diluted with 1 ml DMA and heated for 3.5 h at 85 C. The reaction was cooled, evaporated and partitioned between aqueous saturated NaHCO3/Et2O (3*). The organic phases were washed with aqueous 10% NaCl, dried (NaSO4) and evaporated. Flash chromatography on silica gel (hexane/EtOAc 9:1 to 1:1) gave 1.37 g (69%) of trans-4-{4-[(5-Bromo-pyrimidin-2-yl)-methyl-amino]-cyclohexyl}-but-3-yn-1-ol, MS: 338 (MH+, 1Br).

Reference： [1]Patent: US2003/186984,2003,A1

10
[ 603-35-0 ]
[ 32779-37-6 ]
[ 146631-00-7 ]
[ 152915-90-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; In ethanol; water; toluene;	Example 1 5-bromo-2-[4-(benzoxy)phenyl]pyrimidine STR33 A solution of 104 g of <strong>[32779-37-6]2,5-dibromopyrimidine</strong>, 100 g of 4-benzoxyphenylboronic acid, 4.75 g of Pd (10% on activated charcoal), 4.5 g of triphenylphosphene and 93 g of sodium carbonate in 1 l of toluene, 0.5 l of ethanol and 0.3 l of water is heated at 80 C. for 24 hours. After filtration, the organic phase is separated off and evaporated to dryness in vacuo. The residue is recrystallized from acetonitrile: 83 g of solids of melting point 153-155 C.

Reference： [1]Patent: US5872301,1999,A

11
[ 32779-37-6 ]
[ 156682-54-1 ]
[ 156682-50-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine)palladium (0); In ethanol; water; toluene;	15.00 g (63.10 mmol) of <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (for preparation see: D. W. Arantz and D. J. Brown in Journal of the Chemical Society C, 1971, p. 1889), 14.40 g (63.10 mmol) of 3-benzyloxybenzeneboronic acid, 13.40 g (126.2 mmol) of sodium carbonate and 0.73 g (0.63 mmol) of tetrakis(triphenylphosphine)palladium(0) are heated at 80 C. for 4 hours in 150 ml of toluene, 75 ml of ethanol and 50 ml of water. The reaction mixture is subsequently partitioned between ether and water, the organic phase is washed twice with sodium chloride solution, dried over sodium sulfate and evaporated, and the residue is purified by chromatography (silica gel/dichloromethane), giving 15.14 g of 5-bromo-2-(3-benzyloxyphenyl)pyrimidine. STR14

Reference： [1]Patent: US5447656,1995,A

12
[ 32779-36-5 ]
[ 32779-37-6 ]

Yield	Reaction Conditions	Operation in experiment
62%	In hydrogen bromide; acetic acid;	EXAMPLE 1 A suspension of 67.5 g of 5-bromo-2-chloropyrimidine in 450 ml of 33% by weight hydrogen bromide in glacial acetic acid is heated at 30 C. for 1 hour and then at the boiling temperature for 0.5 hour. The mixture is concentrated in vacuo, the resulting suspension is poured into a 5-fold amount of water, the solid obtained is filtered off and dried. This gives 51.4 g of 2,5-dibromopyrimidine, which corresponds to a yield of 62% of theory, in a purity (HPLC) of>95%. According to the melting point (81-83 C.), IR spectrum and 1 H-NMR spectrum, the product is identical to the 2,5-dibromopyrimidine prepared by the method of J. Org. Chem. 25, 1916 (1960).
	With hydrogen bromide; In acetic acid;	EXAMPLE 2 A suspension of 135 g of 5-bromo-2-chloropyrimidine in 1250 ml of a 33% by weight solution of hydrogen bromide in glacial acetic acid is stirred at 20 C. for 6 hours. After this time, the mixture is poured into a 10-fold amount of water, the precipitated solid is separated off and dried. This gives 117 g of 2,5-dibromopyrimidine which conforms to the specifications of Example 1.

Reference： [1]Patent: US5371224,1994,A
[2]Patent: US5371224,1994,A

13
[ 7440-05-3 ]
[ 32779-37-6 ]
[ 146631-00-7 ]
[ 152915-90-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; In ethanol; water; toluene;	COMPARATIVE EXAMPLE 1 Synthesis of 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine by the process described in DE 39 30 663 4.17 g (17.54 mmol) of <strong>[32779-37-6]2,5-dibromopyrimidine</strong>, 4.00 g (17.54 mmol) of 4-(phenylmethoxy)benzeneboronic acid, 0.19 g (0,175 mmol) of palladium (10%) on activated carbon and 3.72 g (35.10 mmol) of sodium carbonate are reacted in 42 ml of toluene, 21 ml of ethanol and 12.5 ml of water using a similar method to Example 1. Analysis (HPLC) of the crude product indicates a mixture which contains the starting materials <strong>[32779-37-6]2,5-dibromopyrimidine</strong>, 4-(phenylmethoxy)benzeneboronic acid and unidentified products in addition to 6.3% of the desired product 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine. - Example No. R1 A1 A2 A3 A4 R2 Yield Phase transitions 2 H17 C8

Reference： [1]Patent: US5550236,1996,A

14
[ 7440-44-0 ]
[ 32779-37-6 ]
[ 146631-00-7 ]
[ 152915-90-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; triphenylphosphine;palladium; In ethanol; water; toluene;	EXAMPLE 1 5-Bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine 104.25 g (0.438 mol) of <strong>[32779-37-6]2,5-dibromopyrimidine</strong>, 100.00 g (0.438 mol) of 4-(phenylmethoxy)benzeneboronic acid, 4.75 g (0.00438 mol) of palladium (10%) on activated carbon, 4.50 g (0.01752 mol) of triphenylphosphine and 93.00 g (0.876 mol) of sodium carbonate are heated in 1000 ml of toluene, 500 ml of ethanol and 300 ml of water for 24 hours at 80 C. The palladium catalyst is subsequently separated off from the reaction mixture at 80 C. by filtration. The aqueous lower phase of the reaction mixture is separated off at 80 C., before the organic phase is freed of the solvents on a rotary evaporator and dried in a high vacuum. The crude product thus obtained is recrystallized from acetonitrile (3000 ml), giving 150.07 g (97% yield, based on 2,5-dibromopyridine) of 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine (purity according to HPLC: 98%).

Reference： [1]Patent: US5550236,1996,A

15
[ 67-56-1 ]
[ 32779-37-6 ]
[ 14001-66-2 ]

Reference： [1]Journal of Organic Chemistry,2008,vol. 73,p. 9326 - 9333

16
[ 7752-82-1 ]
[ 32779-37-6 ]

Yield	Reaction Conditions	Operation 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: 85-90%; pym: quant; (b) pyr: RCHO, Na(CN)BH3, MeCN, reflux, 1-12h (82%, R = C5Hn); pym: NaH, Rl, THF, rt, overnight (85%, R = Me); (c) Me3(Bn)NBr, f-BuONO, CH2Br2, rt, overnight, pyr: 77-83%; pym: 30- 40%; (d) pym: HI, CH2CI2, 0C, 80-85%; (e) i. NaOH, Br2, H20, rt, 50-60%, ii. POCI3, PhNEt2, reflux, 4h, 75-85%, iii. HI, CH2CI2, 0C, 80-85%; (f) ROH, Na, rt, 1-12 h, quant.; (g) RZnl, CI2Pd(PPh3)2, DMF/THF, rt, overnight, pyr (Br): 72% (R = C6H13), pym (I) 81 %, (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,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,p. 9326 - 9333

17
[ 105-56-6 ]
[ 32779-37-6 ]
[ 65364-66-1 ]

Yield	Reaction Conditions	Operation in experiment
24%		Synthesis of ethyl (5-bromopynmiotadiotan-2-yl)(cvano)acetateTo a chilled stirred suspension of sodium hydride (60% in oil, 34 55 mmol) in tetrahydrofuran (20 mL) was added 1 17g of ethyl cyanoacetate (10 34 mmol) portionwise over 10 minutes After effervescence has ceased, the yellow cloudy mixture was left to warm up to room temperature whilst stirring 2 0O g of 5-bromo,2- bromo-py?midine (10 34mmol) in 3OmL of tetrahydrofuran was added And the mixture was left to stir at room temperature for six hours The resultant brown mixture was concentrated under reduced pressure to give a bright brown precipitate to which water ( 200 mL) was added After extraction with heptane ( 200 mL), the aqueous phase was acidified by the addition of HCl IM and the resultant precipitate was collected by filtration to give on drying ethyl (5 bromopy?midin 2- yl)(cyano)acetate as a b?ght brown powder (0 67g, yield = 24%) 1H NMR delta (ppm, DMSOd6) 3 5 (b, IH), 8 9 (b, IH), 8 45 (b, IH), 4 24 (t, 2H), 1 25 (t, 3H)
24%		Synthesis of ethyl (5-bromopyrimidin-2-yl)(cyano)acetateTo a chilled stirred suspension of sodium hydride (60% in oil, 34.55 mmol) in tetrahydrofuran (20 mL) was added 1.17g of ethyl cyanoacetate (10.34 mmol) portionwise over 10 minutes. After effervescence has ceased, the yellow cloudy mixture was left to warm up to room temperature whilst stirring.2.00 g of 5-bromo,2- bromo-pyrimidine (10.34mmol) in 3OmL of tetrahydrofuran was added. And the mixture was left to stir at room temperature for six hours. The resultant brown mixture was concentrated under reduced pressure to give a bright brown precipitate to which water ( 200 mL) was added. After extraction with heptane ( 200 mL), the aqueous phase was acidified by the addition of HCl IMand the resultant precipitate was collected by filtration to give on drying ethyl (5-bromopyrimidin-2- yl)(cyano)acetate as a bright brown powder (0.67g, yield = 24%). 1R NMR delta (ppm, DMSOd6) : 3.5 (b, IH); 8.9 (b, IH); 8.45 (b, IH); 4.24 (t, 2H); 1.25 (t, 3H).

Reference： [1]Patent: WO2006/117356,2006,A1 .Location in patent: Page/Page column 29
[2]Patent: WO2006/117358,2006,A1 .Location in patent: Page/Page column 37

18
[ 1251583-01-3 ]
[ 32779-37-6 ]
C₂₃H₂₃BrN₆O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; hexane; at -78℃; for 1h;Inert atmosphere;	1,4-dibromopyrazine (350 mg, 1.473 mmol) and 50c (423 mg, 0.982 mmol) are placed in an oven flame-dried round-bottom flask and anhydrous THF (12 mL) is added. The mixture is stirred at RT until a clear solution is obtained. The mixture is stirred under N2 and cooled in a dry-ice/acetone bath (-78 C.) for 15 min. 1.2 M n-BuLi solution in hexanes (1.23 mL, 1.473 mmol) is added dropwise over 50 min. The mixture is then stirred at -78 C. for 1 h. The reaction is quenched with silica gel. Purification using the combiflash eluting with 50/50 EtOAc/Hex followed by 10% MeOH/EtOAc) gives 58a (332 mg, 0.612 mmol).

Reference： [1]Patent: US2010/261714,2010,A1 .Location in patent: Page/Page column 81

19
[ 179942-45-1 ]
[ 32779-37-6 ]
[ 1261072-00-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 90℃; for 16h;Inert atmosphere; sealed tube;	To a stirred solution of 2,5 dibromo pyrimidine (0.32 g, 1.332 mmol), obtained from Preparation 44, in toluene (6 imL) was added 6-(tert-butyl-dimethyl-silanyloxy)-naphthalen-2-yl-boronic acid (0.48 g, 1.585 mmol), EtOH (2 ml_), water (1 ml_) and Na2CO3 (0.35 g, 3.33 mmol). Argon was bubbled through the reaction mixture for 30 minutes. Then Pd(PPh3)4 (0.075 g, 0.065 mmol) was added and the mixture was heated in a sealed tube at 90 0C for 16 hours. The solvent was evaporated under vacuum and the reaction mixture was diluted with ethyl acetate (15 ml_). The ethyl acetate layer was filtered through celite then washed with water (10 ml_) and brine (10 ml_). It was then dried over Na2SO4 and evaporated to dryness. The crude mass was purified by column chromatography on silica gel by using ethyl acetate : hexane (1 :9) mixture to give the title compound as a white solid (546 mg).1H NMR (400 MHz, CDCI3): delta= 8.86 (s, 1 H), 8.83 (s, 1 H), 8.40 (d, 1 H), 7.87 (d, 1 H), 7.76 (d, 1 H), 7.31 (s, 1 H), 7.20 (s, 1 H), 7.10 (dd, 1 H), 1.02 (s, 9H), 0.26 (s, 6H). LCMS (System 1 ) (run time = 5 min): Rt = 3.57 min; m/z 415; 417 [M+H]+

Reference： [1]Patent: WO2011/4276,2011,A1 .Location in patent: Page/Page column 116

20
[ 38353-06-9 ]
[ 32779-37-6 ]

Yield	Reaction Conditions	Operation in experiment
	With phosphorus tribromide; phosphorus(V) oxybromide; at 0℃; for 2.16667h;Reflux;	To a stirred solution of 2-hydroxy-5-bromo pyrimidine (2 g, 11.43 mmol) in PBr3 (6 mL) was added POBr3 (1.4 mL, 13.72 mmol) at 00C. The mixture was stirred for 10 minutes and then refluxed for 2 hours, after which time it was quenched with a saturated solution of sodium bicarbonate at 0 C. It was then diluted with ethyl acetate (40 mL), washed with water (30 mL), followed by brine (20 mL). The organic phase was dried over sodium sulphate and evaporated to dryness. The crude mass was purified by column chromatography on silica gel by using ethyl acetate : hexane (1 :9) mixture to give the title compound as a white solid (1.8 g).1H NMR (400 MHz, DMSO-d6): delta=8.93 (s, 2H). GCMS (System 7) (run time = 13.5 min): Rt = 6.53 min; m/z 238 [M+H]+

Reference： [1]Patent: WO2011/4276,2011,A1 .Location in patent: Page/Page column 115

21
[ 75-89-8 ]
[ 32779-37-6 ]
[ 433683-47-7 ]

Yield	Reaction Conditions	Operation in experiment
49%		Example 73(S)-4-(4-(5-(2,2,2-Trifluoroethoxy)pyrimidin-2-ylamino)phenethyl)-4,5-dihydrooxazol-2-aminea) 5-Bromo-2-(2,2,2-trifluoro-ethoxy)-pyrimidineTo sodium hydride (303 mg) under an argon atmosphere at 0 C. was added dropwise 2,2,2-trifluoroethanol (775 mul) and the mixture was then stirred at RT for 90 min. A solution of <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (1.5 g) in DMF (8 ml) was then added and stirring continued at RT for 2 hours. The reaction mixture was poured into ice (50 mL) and extracted with EtOAc (2×50 mL). The organic layers were dried over MgSO4 and concentrated in vacuo to afford 5-bromo-2-(2,2,2-trifluoro-ethoxy)-pyrimidine (790 mg, 49%) as a yellow oil which was used in the next step without further purification. MS (EI): 258 ([{81Br}M]+), 256 ([{79Br}M]+), 189 ([{81Br}M-CF3]+), 187 ([{79Br}M-CF3]+).

Reference： [1]Patent: US2012/108609,2012,A1 .Location in patent: Page/Page column 36

22
[ 69385-30-4 ]
[ 32779-37-6 ]
[ 1415640-50-4 ]

Yield	Reaction Conditions	Operation in experiment
63%	With N-ethyl-N,N-diisopropylamine; at 120℃; for 0.5h;Microwave irradiation;	Example 53 Preparation of N-(2,6-difluorobenzyl)-5-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)pyrimidin-2-amine (94) A mixture of <strong>[32779-37-6]2,5-dibromopyrimidine</strong> 59 (140 mg, 0.6 mmol), 2,6-difluorobenzylamine (103 mg, 0.72 mmol) and DIEA (2 mL) was heated to 120 C. using microwave irradiation for 0.5 h. The reaction mixture was allowed to cool to ambient temperature and poured in saturated NaHCO3. The product was extracted with EtOAc and purified by flash column. The compound 93 (114 mg, 63%) was obtained as a white solid.

Reference： [1]Patent: US2012/316182,2012,A1 .Location in patent: Page/Page column 102

23
[ 89-99-6 ]
[ 32779-37-6 ]
[ 1341766-40-2 ]

Yield	Reaction Conditions	Operation in experiment
81%	With N-ethyl-N,N-diisopropylamine; at 120℃; for 0.5h;Microwave irradiation;	Example 54 Preparation of N-(2-fluorobenzyl)-5-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)pyrimidin-2-amine (96) A mixture of <strong>[32779-37-6]2,5-dibromopyrimidine</strong> 59 (238 mg, 1 mmol), 2-fluorobenzylamine (125 mg, 0.72 mmol) and DIEA (5 mL) was heated to 120 C. using microwave irradiation for 0.5 h. The reaction mixture was allowed to cool to ambient temperature and poured in saturated NaHCO3. The product was extracted with EtOAc and purified by flash column. Compound 95 (228 mg, 81%) was obtained as white solid.

Reference： [1]Patent: US2012/316182,2012,A1 .Location in patent: Page/Page column 102

24
[ 19064-18-7 ]
[ 32779-37-6 ]
[ 1415640-19-5 ]

Yield	Reaction Conditions	Operation in experiment
48%		Example 33 Preparation of 5-(2,2-difluoro-6-methylbenzo[d]1,3-dioxolen-5-yl)-2-[2,6-difluorophenyl)methoxy]pyrimidine (62) To a solution of 2,6-difluorobenzyl alcohol (288 mg, 2 mmol) in 10 ml dry THF was added sodium hydride (80 mg, 60% mineral oil dispersion, 2 mmol). The resulting suspension was stirred at r.t. for 30 min before addition of <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (476 mg, 2 mmol). After stirred for 1 h at r.t. the reaction mixture was diluted with EA, worked up with aqueous sodium bicarbonate/brine. The organic phase was dried over sodium sulfate, concentrated, subjected to silica gel flash column using hexane and EA as eluents to give 290 mg 60 as white solid (yield: 48%).

Reference： [1]Patent: US2012/316182,2012,A1 .Location in patent: Page/Page column 95

25
[ 38353-09-2 ]
[ 32779-37-6 ]

Yield	Reaction Conditions	Operation 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: 85-90%; pym: quant; (b) pyr: RCHO, Na(CN)BH3, MeCN, reflux, 1-12h (82%, R = C5Hn); pym: NaH, Rl, THF, rt, overnight (85%, R = Me); (c) Me3(Bn)NBr, f-BuONO, CH2Br2, rt, overnight, pyr: 77-83%; pym: 30- 40%; (d) pym: HI, CH2CI2, 0C, 80-85%; (e) i. NaOH, Br2, H20, rt, 50-60%, ii. POCI3, PhNEt2, reflux, 4h, 75-85%, iii. HI, CH2CI2, 0C, 80-85%; (f) ROH, Na, rt, 1-12 h, quant.; (g) RZnl, CI2Pd(PPh3)2, DMF/THF, rt, overnight, pyr (Br): 72% (R = C6H13), pym (I) 81 %, (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

26
[ 39211-55-7 ]
[ 32779-37-6 ]
[ 1428558-46-6 ]

Yield	Reaction Conditions	Operation in experiment
64%	With N-ethyl-N,N-diisopropylamine; In butan-1-ol; at 120℃; for 12h;	5-bromo-N-(3-chloro-4-(difluoromethoxy)phenyl)pyrimidin-2-amine To a solution of 3-chloro-4-(difluoromethoxy)aniline (0.814 g, 4.20 mmol) in butan-1-ol (10 mL), were added DIPEA (2.203 mL, 12.61 mmol) and <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (1 g, 4.20 mmol). The reaction mixture was stirred at 120 C. for 12 h and concentrated. The crude product was purified by flash chromatography on silica gel using 3% ethyl acetate in petroleum ether to give 5-bromo-N-(3-chloro-4-(difluoromethoxy)phenyl)pyrimidin-2-amine (0.8 g, 64%). LCMS (ES-ES), m/z 349.98.

Reference： [1]Patent: US2013/79338,2013,A1 .Location in patent: Paragraph 0167; 0168

27
[ 944392-68-1 ]
[ 32779-37-6 ]
[ 1601485-39-5 ]

Yield	Reaction Conditions	Operation in experiment
56%	With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 80℃; for 48h;Inert atmosphere;	Tetramethyl 5,5'-(pyrimidine-2,5-diyl)diisophthalate 2,5-Dibromopyrimidine (1.18 g, 5 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) isophthalate (3.52 g, 11 mmol), K3PO4 (2.55 g, 12 mmol) and tetrakis(triphenylphosphine) palladium(0) (0.3 g, 0.26 mmol) were dissolved in dry 1,4-dioxane (80 mL) under N2 atmosphere. The mixture was stirred at 80 C. for two days. After that, the precipitate was collected by filtration, washed with 1,4-dioxane for several times, and then recrystallized in toluene to obtain the pure product. Yield: 56% (1.3 g). 1H NMR (500 MHz, CDCl3, ppm): delta 9.38 (s, 2H), 9.15 (s, 2H), 8.86 (s, 1H), 8.80 (s, 1H), 8.53 (s, 2H), 4.03 (s, 12H).

Reference： [1]Journal of the American Chemical Society,2014,vol. 136,p. 6207 - 6210
[2]Patent: US2017/173559,2017,A1 .Location in patent: Paragraph 0064; 0065

28
[ 785051-54-9 ]
[ 32779-37-6 ]
9,9'-(pyrimidine-2,5-diylbis(4,1-phenylene))bis(9H-carbazole) [ No CAS ]

Reference： [1]RSC Advances,2015,vol. 5,p. 17030 - 17033

29
[ 870119-58-7 ]
[ 32779-37-6 ]
9,9'-(pyrimidine-2,5-diylbis(3,1-phenylene))bis(9H-carbazole) [ No CAS ]

Reference： [1]RSC Advances,2015,vol. 5,p. 17030 - 17033

30
[ 7589-27-7 ]
[ 32779-37-6 ]
5-bromo-2-(4-fluorophenethoxyl)pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
0.7 g		j0120] To a solution of2-(4-fluorophenyl)ethanol (0.566 g) in TRF (10 mE) was added NaR (0.269 g). The mixture was stirred at room temperature for 2 hours, before 2,5-dibro- mopyrimidine (0.8 g) was added. The mixture was stirred at room temperature for 16 h. The reaction was quenched with water and extracted with EtOAc (2x20 mE). The organic layers were combined, dried over MgSO4 and concentrated under vacuum. The residue was purified by silica gel column (Rex/EtOAc=1 00:5) to give 5-bromo-2-(4-fluoropheneth- oxyl)pyrimidine (0.7 g). ECMS (M+R)=297.0.

Reference： [1]Patent: US2015/232463,2015,A1 .Location in patent: Paragraph 0120

31
[ 913835-67-3 ]
[ 32779-37-6 ]
di-tert-butyl 2,2'-(pyrimidine-2,5-diyl)bis(6-cyano-1H-indole-1-carboxylate) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
142 mg	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; water; for 5h;Heating; Inert atmosphere;	A mixture ofcompound 6 (0.31 g, 0.84 mmol), <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (0.10 g, 0.42 mmol), palladium tetrakis (146 mg, 0.13 mmol) and sodium carbonate (0.27 g, 2.53 mmol) in 1,2-dimethoxyethane (12 mL) and water (3mL) was stirred under Ar and heated to 78 oC for 5 h. The suspension was allowed to cool to 20 C. Ethylacetate (30 mL) and water (10 mL) were added. The organic layer was separated. The aqueous solutionwas extracted with ethyl acetate (10 mL). The combined organic solutions were washed with brine,dried over MgSO4 and concentrated. The residue was dissolved in 2 mL of dichloromethane and loadedon a silica gel column; elution with hexanes/ethyl acetate (1/0 to 0/1) provided (I-4) (142 mg) as yellowsolid, which was used for the next step without further purification. Rf 0.20 and 0.10 (25% ethyl acetatein hexanes) [UV].

Reference： [1]Bioorganic and Medicinal Chemistry,2015,vol. 23,p. 5789 - 5798

32
[ 56041-85-1 ]
[ 32779-37-6 ]
C₂₂H₁₆N₂S₂ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2015,vol. 137,p. 13818 - 13826

33
[ 500556-90-1 ]
[ 32779-37-6 ]
(1S,2R,4R)-tert-butyl 2-((5-bromopyrimidin-2-yl)amino)-7-azabicyclo[2.2.1]heptane-7-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With N-ethyl-N,N-diisopropylamine; In N,N-dimethyl acetamide; at 120℃; for 0.5h;Microwave irradiation;	11126] To a solution of intermediate B-S (520 g, 2.45 mmol) in DMA (8.2 mE) was added DIPEA (0.84 mE, 4.90 mmol) followed by <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (661 g, 2.69 mmol). The reaction mixture was heated at 120 C. for 30 minutes using microwave and was then diluted with water and EtOAc. The aqueous phase was extracted twice with EtOAc and the combined organic layers were washed with a saturated solution of NaC1, dried over Mg504, filtered and evaporated. Purification via silica gel chromatography (0-40% EtOAc in hexanes) gave the title compound (651 g, 72%). MS (ESI): mass calcd. for C,5H2,BrN4O2, 368.1; m/z found, 370.9 [M+H]. ?H NMR (500 MHz, CDC13) oe 8.28 (is, 2H),5.56 (s, 1H), 4.29 (s, 1H), 4.23-4.15 (m, 1H), 3.99-3.91 (m, 1H), 2.03-1.93 (m, 1H), 1.87-1.63 (m, 2H), 1.62-1.32 (m, 12H).

Reference： [1]Patent: US2016/46640,2016,A1 .Location in patent: Paragraph 1126

34
1-(5-benzyloxy-2-nitrophenyl)-1-tributylstannylethene [ No CAS ]
[ 32779-37-6 ]
[ 625119-87-1 ]
2,3-di(5-benzyloxy-2-nitrophenyl)-1,3-butadiene [ No CAS ]
1-(5-benzyloxy-2-nitrophenyl)-1-(2-pyrimidyl)ethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
10%; < 9%; 27%	With copper(l) iodide; triphenylphosphine; bis(dibenzylideneacetone)-palladium(0); In N,N-dimethyl-formamide; at 100℃; for 48h;Inert atmosphere;	General procedure: To a solution of 2,5-dibromopyrazine (5) (100 mg, 0.420 mmol) and 4 (458 mg, 0.841 mmol) in dry DMF (2 mL) was added bis(dibenzylideneacetone)palladium (Pd(dba)2, 19.4 mg, 0.034 mmol), CuI (160 mg, 0.841 mmol), and PPh3 (35.3 mg, 0.135 mmol) respectively. The resulting brown mixture was stirred under an atmosphere of N2 at 90 C for 41 h. EtOAc (25 mL) was added and the mixture was washed with H2O (325 mL) and brine (325 mL). The organic layer was dried (MgSO4), filtered, and the solvents were removed under reduced pressure. The residue was purified by chromatography on SiO2/K2CO3 (10% K2CO3, EtOAc/hexane, 1:9, then 2:8.

Reference： [1]Tetrahedron,2016,vol. 72,p. 4214 - 4221

35
[ 32779-37-6 ]
[ 1066-54-2 ]
2,5-di(2-trimethylsilylethynyl)pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%		5-Benzyloxy-2-nitro-1-bromobenzene 41 (1) (3.91 g, 12.7 mmol) was dissolved in toluene (10 mL) and triethylamine (NEt3, 40 mL) whereby bis(triphenylphosphinepalladium dichloride (PdCl2(PPh3)2, 0.62 g, 0.88 mmol) and copper iodide (CuI, 0.17 g, 0.89 mmol) were added successively. The reaction mixture was stirred under a nitrogen atmosphere for five minutes. Trimethylsilylethyne (2.17 mL, 15.2 mmol) was added drop wise and the resulting mixture was stirred at 48 C for 24 h. After cooling to ambient temperature, the mixture was filtered through Celite, and the Celite was washed with EtOAc. The solvents were removed from the filtrate under reduced pressure. The resulting residue was purified by chromatography (EtOAc/hexane, 1:9) affording 2 (3.71 g, 11.4 mmol, 90%) as a faint yellow solid. Mp=96 C; 1H NMR (400 MHz, CDCl3) delta 8.07 (d, J=9.2 Hz, 1H), 7.43-7.36 (m, 5H), 7.18 (d, J=2.8 Hz, 1H), 6.97 (dd, J=9.2, 2.8 Hz, 1H), 5.14 (s, 2H), 0.29 (s, 9H); 13C NMR (100 MHz, CDCl3) delta 161.8, 143.2, 135.3, 128.8, 128.5, 127.5, 127.0, 120.7, 120.1, 115.4, 103.7, 99.9, 70.7, 0.4; IR (APT) 1572, 1515, 1333. 1248, 836 cm-1; HRMS (ESI) calcd for C18H20NO3Si (M+H+) 326.1212, found 326.1195.

Reference： [1]Tetrahedron,2016,vol. 72,p. 4214 - 4221

36
[ 75927-49-0 ]
[ 32779-37-6 ]
[ 883901-68-6 ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; In 1,4-dioxane; water; at 90℃; for 12h;Inert atmosphere;	To a solution of 2, 5-dibromopyrimidine (2.0 g, 8.41 mmol), 4,4,5, 5-tetramethyl-2- vinyl-l,3,2-dioxaborolane (1.56 g, 10.09 mmol), and Pd(dppf)C12 (0.31 g, 0.42 mmol) in dioxane (20 mL) and water (2 mL) was added Na2CC>3 (1.782 g, 16.82 mmol) under N2. The resulting mixture was stirred at 90 C for 12 h. After cooling to RT, the mixture was diluted with water and extracted with EtOAc (100 mL x 3). The combined organic layers were dried over MgS04, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography (2-30% EtOAc in petroleum ether) to give the title compound as a oil. LRMS m/z (M+H) 185.1, 187.1 found, 185.1, 187.1 required.

Reference： [1]Patent: WO2016/100156,2016,A1 .Location in patent: Page/Page column 56; 57

37
[ 1227040-87-0 ]
[ 32779-37-6 ]
C₅₆H₄₀N₂ [ No CAS ]

Reference： [1]Journal of Materials Chemistry C,2016,vol. 4,p. 7640 - 7648

38
5-phenyl-5,7-dihydroindolo[2,3-b]carbazole [ No CAS ]
[ 32779-37-6 ]
C₂₈H₁₇BrN₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85.8%	With dmap; potassium carbonate; In N,N-dimethyl-formamide; at 50℃; for 8h;	Preparation of compound 5-1[231]After introducing 12H-benzo[4,5]thieno[2,3-a]carbazole (20 g, 60.2 mmol), <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (7.4 g, 50.2 mmol), dimethylaminopyridine (DMAP) (367 mg, 3.01 mmol), K2CO3(25 g, 180.3 mmol), and dimethylformamide (DMF) 200 mL into a flask, the mixture was stirred at 50C for 8 hours. After the reaction is completed, an organic layer was extracted with ethyl acetate, and remaining moisture was removed with magnesium sulfate and dried. The remaining product was then separated with column chromatography to obtain compound 5-1 (23 g, 85.8%).

Reference： [1]Patent: WO2016/186321,2016,A1 .Location in patent: Paragraph 230-231

39
1-methyl-3-((triisopropylsilyl)ethynyl)-1H-pyrazol-4-amine [ No CAS ]
[ 32779-37-6 ]
5-bromo-N-(1-methyl-3-((triisopropylsilyl)ethynyl)-1H-pyrazol-4-yl)pyrimidin-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine; In dimethyl sulfoxide; at 120℃;Inert atmosphere;	To a solution of <strong>[32779-37-6]2,5-dibromo-pyrimidine</strong> (385 mg, 1.62 mmol) and 1-methyl-3-((triisopropylsilyl)ethynyl)-1H-pyrazol-4-amine (300 mg, 1.08 mmol) in DM80 (20 mE) wasadded DIEA (279 mg, 2.16 mmol), and the mixture was stirred at 120 C ovemight under N2.After cooling to it, the mixture was purified by reverse phase chromatography (Welch UltimateXB-C18, 40-70 jim) eluting with a gradient of 60-95% acetonitrile in water to afford 5-bromo-N-( 1 -methyl-3 -((triisopropyL silyl)ethynyl)- 1JJ-pyrazol-4-yl)pyrimidin-2-amine.

Reference： [1]Patent: WO2017/19804,2017,A2 .Location in patent: Paragraph 0386

40
[ 32779-37-6 ]
[ 66787-73-3 ]
tert-butyl (5-bromopyrimidin-2-yl)(1-methyl-1H-imidazol-5-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20%	With caesium carbonate; In N,N-dimethyl-formamide; at 60℃;Inert atmosphere;	To a solution of <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (605 mg, 2.54 mmol) and tert-butyl (1-methyl-1H-imidazol-5-yl)carbamate (500 mg, 2.54 mmol) in DMF (10 mL) was added Cs2CO3 (1.66 g, 5.09 mmol). The mixture was heated at 60 C overnight under nitrogen, cooled to ii, and added to water (10 mL). The mixture was extracted with EtOAc (3 x 10 mL) and the combined organic layers were washed with brine (5 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by reverse phase flash chromatography (Welch Ultimate XB-C 18, 40-70 jim) eluting with a gradient of 10-95% acetonitrile in water to afford tert-butyl (5-bromopyrimidin-2-yl)(1 -methyl- 1H-imidazol-5 - yl)carbamate as a yellow solid (180 mg, 20%).

Reference： [1]Patent: WO2017/19804,2017,A2 .Location in patent: Paragraph 0301

41
3,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,8-bis[2-(tertbutyldimethylsilanyloxy)ethyl]-dibenzothiophene-S,S-dioxide [ No CAS ]
[ 32779-37-6 ]
3,7-bis(5-bromopyrimidin-2-yl)-2,8-bis[2-(tertbutyldimethylsilanyloxy)ethyl]dibenzothiophene-S,S-dioxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
500 mg	With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate; In water; at 85℃;Inert atmosphere;	The crude product 7 (1.00 g), <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (730 mg,3.10 mmol), TBAB (30 mg), toluene (15 mL), aqueous solution ofK2CO3 (2 M, 4.00 mL) and Pd(PPh3)4 (45.0 mg, 0.0400 mmol) were added into a 50 mL of three-neck flask under argon. The reactio nwas heated to 85 C and stirred overnight. Then the reaction was cooled to room temperature and mixed with distilled water(35 mL). The aqueous layer was extracted with ethyl acetate forthree times. The combined organic layer was washed with distilledwater and brine before dried over anhydrous MgSO4. The organicsolvent was distilled and the crude product was purified by columnchromatography with ethyl acetate/petroleum ether (1/1, v/v) aseluent to afford 8 as a white solid (500 mg). 1H NMR (300 MHz,CDCl3) d (ppm): 8.92 (s, 4H), 8.47 (s, 2H), 7.85 (s, 2H), 3.93e3.91 (t,J 3 Hz, 4H), 3.35e3.32 (t, J 4.5 Hz, 4H), 0.87 (s, 18H), 0.03 (s,12H). 13C NMR (75 MHz, CDCl3) d (ppm): 163.41, 157.83, 145.72,138.96, 136.82, 131.54, 125.59, 125.21, 119.08, 63.68, 37.82, 25.94,18.30, 5.37. MS (APCI) calculated for C36H46Br2N4O4SSi2: 846.8,found: 847.4. Elemental analysis calculated for C36H46Br2N4O4SSi2:C, 51.06; H, 5.48; N, 6.62; S, 3.79, found: C, 51.68; H, 5.99; N, 6.36; S,3.52.

Reference： [1]Tetrahedron,2017,vol. 73,p. 2649 - 2655

42
[ 134179-38-7 ]
[ 32779-37-6 ]
N-(2-{2-[2-(2-azidoethoxy)ethoxy]ethoxy}ethyl)-5-bromopyrimidin-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With potassium carbonate; In dimethyl sulfoxide; at 100℃; for 3h;	(1) To a solution of 2-{2-[2-(2-azidoethoxy)ethoxy]ethoxy}ethanamine (1.5 g) in dimethyl sulfoxide (80 mL), <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (1.7 g) and potassium carbonate (1.9 g) were added, and the mixture was stirred at 100C for 3 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. The organic layer wasdried over anhydrous magnesium sulfate and filtered, and then, the filtrate was concentrated under reduced pressure.The obtained residue was purified by silica gel column chromatography (Biotage(registered trademark) SNAP Cartridge HP-Sphere, hexane:ethyl acetate = 100:0 ? 0:100) to obtain N-(2-{2-[2-(2-azidoethoxy)ethoxy]ethoxy}ethyl)-5-bromopyrimidin-2-amine (2.1 g, 81%). LC-MS Retention Time 0.849 min LC:Agilent 1290ESI/APCI MS:Agilent 6130 Column: Waters Acquity CSH C18 1.7um, 2.1x50mm Solvent: H2O:CH3CN(0.1% Formic acid) Gradient: 0.8mL/min, 0min(80:20) ? 1.2-1.4min(1:99) MS (+): 375, 377 [M+H]+.

Reference： [1]Patent: EP3173408,2017,A1 .Location in patent: Paragraph 0332

43
[ 32779-37-6 ]
[ 153086-78-3 ]
tert-butyl [2-(2-{2-[(5-bromopyrimidin-2-yl)amino]ethoxy}ethoxy)ethyl]carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium carbonate; In dimethyl sulfoxide; at 100℃; for 2h;	(1) To a solution of tert-butyl {2-[2-(2-aminoethoxy)ethoxy]ethyl}carbamate (0.40 g) in dimethyl sulfoxide (5.0 mL),potassium carbonate (0.45 g) and <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (0.38 g) were added, and the mixture was stirred at 100C for 2 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. The organic laye rwas dried over anhydrous magnesium sulfate and filtered, and then, the filtrate was concentrated under reducedpressure. The obtained residue was purified by silica gel column chromatography (Biotage(registered trademark) SNAP Cartridge HP-Sphere, hexane:ethyl acetate = 100:0 ? 20:80) to obtain tert-butyl [2-(2-{2-[(5-bromopyrimidin-2-yl)amino]ethoxy}ethoxy)ethyl]carbamate (0.51 g, 78%) as a colorless amorphous substance. LC-MS Retention Time 0.928 min LC:Agilent 1290ESI/APCI MS:Agilent 6130 Column: Waters Acquity CSH C18 1.7um, 2.1x50mm Solvent: H2O:CH3CN(0.1% Formic acid) Gradient: 0.8mL/min, 0min(80:20) ? 1.2-1.4min(1:99) MS (+): 405 [M+H]+.

Reference： [1]Patent: EP3173408,2017,A1 .Location in patent: Paragraph 0324

44
(1-(4-fluoro-3-(trifluoromethyl)phenyl)-1H-1,2,3-triazol-4-yl)m ethanol [ No CAS ]
[ 32779-37-6 ]
5-bromo-2-((1-(4-fluoro-3-(trifluoromethyl)phenyl)-1H-1,2,3-triazol-4-yl)methoxy)pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate; In acetonitrile; at 110℃;	General procedure: A solution of (1-(3-(difluoromethyl)-4-fluorophenyl)-1 H-i ,2,3-triazol-4- yl)methanol (Intermediate 9, 110 mg, 0.41 mmol), Cs2CO3 (535.9 mg, 1.64 mmol), and i-(2-chloropyrimidin-5-yl)ethan-i-one (83.6 mg, 0.53 mmol) in ACN (0.02 mL) was heated at 110 C overnight. The reaction mixture wascooled, diluted with EtOAc, and washed with sat. aq. NH4CI. The organic layer was dried (Na2504), filtered, and concentrated under reduced pressure. Purification (FCC, 5i02, 0-50% EtOAc in hexanes) afforded the title compound (12 mg, 8%).

Reference： [1]Patent: WO2017/139428,2017,A1 .Location in patent: Page/Page column 199; 349

45
tert-butyl 2-(((tert-butyldiphenylsilyl)oxy)methyl)piperazine-1-carboxylate [ No CAS ]
[ 32779-37-6 ]
tert-butyl 4-(5-bromopyrimidin-2-yl)-2-(((tert-butyldiphenylsilyl)oxy)methyl)piperazine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With potassium carbonate; In acetonitrile; at 75℃; for 4h;	[00471] 2,5-Dibromopyrimidine (4.32 g, 18.2 mmol, 1.0 equiv) and butyldiphenylsilyl)oxy)methyl)piperazine-l-carboxylate (10 g, 21.9 mmol, 1.2 equiv) were dissolved in MeCN (91.0 mL). Next potassium carbonate (5.04 g, 36.5 mmol, 2.0 equiv) was added. The reaction was heated at 75 C for 4 h. The reaction was then filtered and concentrated under reduced pressure to a white foam. The foam was purified by silica gel chromatography (0?5% EtOAc/heptane) to yield the product as a white solid (10.2 g, 92% yield). LCMS (ESI) m/z: [M + H] calcd for 611.20; found 611.0.

Reference： [1]Patent: WO2018/204416,2018,A1 .Location in patent: Paragraph 00471

46
[ 86-74-8 ]
[ 32779-37-6 ]
C₁₆H₁₀BrN₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%		Sodium hydride (0.264 g, 11 mmol), carbazole (1.67 g, 10 mmol), removablenitrogen three times, was added 30 ml DMF in an ice water bath, ice water bath maintaining the reaction 1 h.<strong>[32779-37-6]2,5-dibromo-pyrimidine</strong> (2.855 g, 12 mmol; dissolved in 15 ml DMF) was added to the reaction mixture, thereaction was heated to 130. deg.] C for 12 hours. The mixture was then cooled to room temperature, thereaction solution was poured into 300 ml ice water, filtered, the filter residue dissolved in methylene chloride,dried over anhydrous sodium sulfate, the filtrate was mixed with silica gel by column to give a white product(1.944 g, 60%).

Reference： [1]Patent: CN109053692,2018,A .Location in patent: Paragraph 0024; 0025

47
6-(5-methoxy-2-methylphenyl)-5,6,7,8-tetrahydrophthalazin-1(2H)-one [ No CAS ]
[ 32779-37-6 ]
2-(5-bromopyrimidin-2-yl)-6-(5-methoxy-2-methylphenyl)-5,6,7,8-tetrahydrophthalazin-1(2H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50.61%	With potassium phosphate; copper(l) iodide; N,N-dimethylethylenediamine; In 1,4-dioxane; at 25 - 110℃; for 12.0833h;Inert atmosphere;	According to Scheme 9, step i: To a mixture of Intermediate 7c (0.1 g, 369.92 umol, 1 eq) and 2, 5-dibromopyrimidine(263.99 mg, 1.11 mmol, 3 eq) in dioxane (20 mL) was added Cul (35.23 mg, 184.96 umol, 0.5 eq), K3PO4(196.31 mg, 924.81 umol, 2.5 eq) and DMEDA (16.30 mg, 184.96 umol, 0.5 eq) in one portion at 25C under N2. Themixture was stirred at 25C for 5 min, then heated to 110C and stirred for 12 hours. The reaction mixture was filteredand the filter was concentrated. The residue was purified by silica gel chromatography (Petroleum ether/Ethyl acetate=15/1?1/1) to provide intermediate 52a (0.08 g, 187.22 umol, 50.61 % yield) as a yellow solid. 1H NMR: (CDCl3, 400MHz) H) delta 8.88 (s, 2H), 7.61 (s, 1 H), 7.05 (d, J = 8.4 Hz, 1 H), 6.75-6.58 (m, 2H), 3.73 (s, 3H), 3.07-2.85 (m, 2H),2.75-2.65 (m, 1 H), 2.61-2.57 (m, 2H), 2.23 (s, 3H), 2.08-2.05 (m, 1 H), 1.81-1.76 (m, 1 H).

Reference： [1]Patent: EP3459939,2019,A1 .Location in patent: Paragraph 0434

48
6-fluoro-5-(piperidin-4-yl)-5H-imidazo[5,1-a]isoindole ditrifluoroacetate [ No CAS ]
[ 32779-37-6 ]
5-(1-(5-bromopyrimidin-2-yl)piperidin-4-yl)-6-fluoro-5H-imidazo[5,1-a]isoindole [ No CAS ]

Reference： [1]ACS Medicinal Chemistry Letters,2019,vol. 10,p. 949 - 953

49
[ 32779-37-6 ]
[ 57260-71-6 ]
[ 374930-88-8 ]

Yield	Reaction Conditions	Operation in experiment
88%	With potassium carbonate; In acetonitrile; at 80℃; for 12h;Sealed tube; Inert atmosphere;	General procedure: In a dry sealed tube under argon were placed, to a solution of 1-Boc-piperazine (5.04 mmol), potassium carbonate (13.1 mmol) in acetonitrile (12.6 mL) was added 2,5-dibromo pyrimidine13(5.04 mmol). The mixture was allowed to stir at 80 C for 12 h. After completion of the reaction (monitored by TLC), the mixture was then cooled at room temperature, then it was quenched with saturated aqueous NH4Cl (10 mL) and extracted with EtOAc. The organic layers were dried over anhydrous MgSO4and concentrated in vacuo. The resulting residue was purified by flash column chromatography on silica gel (EtOAc:n-hexane = 1:8) to afford piperazine11a. tert-Butyl 4-(5-bromopyrimidin-2-yl)piperazine-1-carboxylate(11a): Yield: 88%;1H-NMR (400 MHz, CDCl3)delta8.30 (s,J= 2.0 Hz, 2H), 3.78-3.75 (t,J= 5.2 Hz, 4H), 3.49-3.47 (t,J= 5.2 Hz, 4H), 1.48 (s, 9H).13C-NMR (100 MHz, CD3OD)delta161.2, 159.2, 156.46, 107.15, 81.5, 44.8, 28.6.

Reference： [1]Molecules,2019,vol. 24

50
[ 32779-37-6 ]
[ 163765-44-4 ]
[ 1272973-68-8 ]

Yield	Reaction Conditions	Operation in experiment
92%	With potassium carbonate; In acetonitrile; at 80℃; for 12h;Sealed tube; Inert atmosphere;	General procedure: In a dry sealed tube under argon were placed, to a solution of 1-Boc-piperazine (5.04 mmol), potassium carbonate (13.1 mmol) in acetonitrile (12.6 mL) was added 2,5-dibromo pyrimidine13(5.04 mmol). The mixture was allowed to stir at 80 C for 12 h. After completion of the reaction (monitored by TLC), the mixture was then cooled at room temperature, then it was quenched with saturated aqueous NH4Cl (10 mL) and extracted with EtOAc. The organic layers were dried over anhydrous MgSO4and concentrated in vacuo. The resulting residue was purified by flash column chromatography on silica gel (EtOAc:n-hexane = 1:8) to afford piperazine11a.

Reference： [1]Molecules,2019,vol. 24

51
[ 32779-37-6 ]
[ 112275-50-0 ]
[ 1374144-73-6 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium carbonate; In acetonitrile; at 80℃; for 12h;Sealed tube; Inert atmosphere;	General procedure: In a dry sealed tube under argon were placed, to a solution of 1-Boc-piperazine (5.04 mmol), potassium carbonate (13.1 mmol) in acetonitrile (12.6 mL) was added 2,5-dibromo pyrimidine13(5.04 mmol). The mixture was allowed to stir at 80 C for 12 h. After completion of the reaction (monitored by TLC), the mixture was then cooled at room temperature, then it was quenched with saturated aqueous NH4Cl (10 mL) and extracted with EtOAc. The organic layers were dried over anhydrous MgSO4and concentrated in vacuo. The resulting residue was purified by flash column chromatography on silica gel (EtOAc:n-hexane = 1:8) to afford piperazine11a.

Reference： [1]Molecules,2019,vol. 24

52
[ 1256359-99-5 ]
[ 32779-37-6 ]
C₁₈H₁₈BrN₃O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
3.45 g	With caesium carbonate; In 1,4-dioxane; at 100℃;Inert atmosphere;	In a 250 mL round bottom flask, N-Boc-3-iodo-5-methoxyindole 1a (5 g, 13.4 mmol) and tetrakis (triphenylphosphine) palladium (0.53 g, 0.4 mmol) were dissolved in 50 mL 1 , 4-dioxane, replacement gas.Triethylamine (19 mL, 134 mmol) and pinacol borane (3 mL, 20.1 mmol) were added with a syringe, and the mixture was stirred at 80 C after the dropwise addition.Stop heating after 3h, and after cooling to room temperature, add <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (3.2g, 13.4mmol) to the system under the protection of argonCesium carbonate (10.9 g, 33.5 mmol). After the addition was complete, the system was stirred at 100 C. overnight and monitored by TLC.After the reaction was completed, spin-dry column chromatography (V petroleum ether: V ethyl acetate = 100: 1 ? V petroleum ether: V ethyl acetate = 20: 1) to obtain 3.45 g of a white solid with a yield of 65%.

Reference： [1]Patent: CN110759893,2020,A .Location in patent: Paragraph 0034-0036

53
[ 32779-37-6 ]
[ 214360-73-3 ]
4-(5-bromopyrimidin-2-yl)aniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 2.5h;	<strong>[32779-37-6]2,5-dibromopyrimidine</strong> (2 g, 8.41 mmol)And 4-aminophenylboronic acid pinacol ester (2.3 g, 10.51 mmol)Was dissolved in 1,4-dioxane solution, and then Pd(PPh3)4 (484 mg, 0.42 mmol)And 2.0 M potassium phosphate aqueous solution (12.6 mL, 25.2 mmol)Was added.The reaction mixture at 90CStir for 2.5 hours.When the reaction was completed, extraction was performed using distilled water and ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the concentrate was purified by column chromatography to give 1.8 g (68% yield) of the title compound.
68%	With potassium dihydrogenphosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 2.5h;	2,5-Dibromopyrimidine (2 g, 8.41 mmol) and 4-aminophenylboronic acid pinacol ester (2.3 g, 10.51 mmol) were dissolved in a 1,4-dioxane solution, and then Pd(PPh3)4 (484 mg, 0.42 mmol) and a 2.0 M aqueous potassium phosphate solution (12.6 mL, 25.2 mmol) were added to obtain a reaction mixture. The reaction mixture was stirred at 90C for 2.5 hours. When the reaction was completed, the reaction product was extracted using distilled water and ethyl acetate to obtain an organic layer, and the organic layer was dried over anhydrous magnesium sulfate and then filtered. The filtrate was concentrated under reduced pressure, and the concentrate was purified by column chromatography to obtain 1.8 g (68% yield) of the title compound.

Reference： [1]Patent: KR2020/76655,2020,A .Location in patent: Paragraph 1814; 1816-1818
[2]Patent: EP3901139,2021,A1 .Location in patent: Paragraph 0385

54
[ 5467-74-3 ]
[ 32779-37-6 ]
[ 1263061-48-8 ]

Reference： [1]Chemical Communications,2020,vol. 56,p. 13117 - 13120

55
[ 623-51-8 ]
[ 32779-37-6 ]
ethyl 2-((2-bromopyrimidin-5-yl)thio)acetate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2021,vol. 60,p. 3708 - 3713
Angew. Chem.,2021,vol. 133,p. 3752 - 3757,6

56
[ 98-02-2 ]
[ 32779-37-6 ]
2-bromo-5-((furan-2-ylmethyl)thio)pyrimidine [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2021,vol. 60,p. 3708 - 3713
Angew. Chem.,2021,vol. 133,p. 3752 - 3757,6

57
5-fluoro-2-methoxy-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline [ No CAS ]
[ 32779-37-6 ]
3-(5-bromopyrimidin-2-yl)-5-fluoro-2-methoxyaniline [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2021,vol. 64,p. 677 - 694

58
(4-aminophenyl)boronic acid hydrochloride [ No CAS ]
[ 32779-37-6 ]
[ 102570-64-9 ]

Yield	Reaction Conditions	Operation in experiment
83%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In water; toluene; at 110℃;Inert atmosphere; Schlenk technique;	Under the protection of argon, the 4-aminobenzene borate hydrochloride (0.066mol, 11.44g), <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (0.03mol, 7.14g), bis(triphenylphosphine) palladium dichloride (0.003mol, 2.10g), anhydrous potassium carbonate (0.3mol, 41.46g), 50mL toluene and 50mL deionized water were sequentially added to a 250mL round-bottomed flask, the reaction system was stirred and refluxed at 110C, TLC monitored until 2, The 5-dibromopyrimidine disappeared completely, the reaction was stopped, a large amount of solids precipitated out after cooling to room temperature, the solids were filtered and washed with deionized water, toluene and methanol several times, and dried in vacuum to obtain a crude product; after the crude product was purified, Finally, 6.50 g of yellow crystals, namely 2,5-bis(4-aminophenyl)pyrimidine, were obtained with a yield of 83%.

Reference： [1]Patent: CN112679418,2021,A .Location in patent: Paragraph 0078-0082

59
[ 64099-82-7 ]
[ 32779-37-6 ]
5-bromo-2-propynylpyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53.5%	With bis-triphenylphosphine-palladium(II) chloride; In 1,4-dioxane; at 80℃; for 3h;Inert atmosphere;	2,5-Dibromopyrimidine (9.0g, 38.1mmol), tributyl(1-propynyl)tin (16.3g, 49.6mmol), Pd(PPh3)2Cl2 (5.3g, 7.6mmol), dissolved in 1,4- Dioxane (90mL), under the protection of N2, react at 80C for 3h. After the reaction is complete, add saturated NaOH solution and saturated NaHCO3 solution and stir for 30 min,Add water (50mL), extract with EA three times (3*100mL), combine the organic phases, dry over anhydrous Na2SO4, filter, spin dry,After normal phase preparative chromatography (EA:PE=1:5), the product (4.0g, yield 53.5%) was obtained.

Reference： [1]Patent: CN112574211,2021,A .Location in patent: Paragraph 0241-0244

60
[ 32779-37-6 ]
[ 105-53-3 ]
[ 66621-92-9 ]

Yield	Reaction Conditions	Operation in experiment
		Under nitrogen protection, put 16g (0.1mol) of diethyl malonate and 100mL of tetrahydrofuran into the reaction flask and mix, cool down to -5C, and add 20% potassium tert-butoxide/ 61.7 g (0.11 mol) of tetrahydrofuran solution, react at 0C for 0.5 hours after dropping, and then dropwise add a mixed solution containing 23.8 g (0.1 mol) of <strong>[32779-37-6]2,5-dibromopyrimidine</strong>/30 mL of tetrahydrofuran, slowly warm up to room temperature after dropping, and react After 1 hour, the raw material was less than 1.5% by sampling HPLC.

Reference： [1]Patent: CN113683571,2021,A .Location in patent: Paragraph 0041-0043

61
[ 1011460-68-6 ]
[ 32779-37-6 ]
5-bromo-2-[1-(trifluoromethyl)vinyl]pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II) dichloromethane adduct; potassium carbonate; In 1,4-dioxane; water monomer; at 80℃; for 12h;Inert atmosphere;	To a solution of 1-(trifluoromethyl)vinylboronic acid hexylene glycol ester (4.7 g, 21.19 mmol, 1.2 equiv; CAS RN 1011460-68-6) and <strong>[32779-37-6]2,5-dibromopyrimidine</strong> (4.2 g, 17.66 mmol, 1.0 equiv), potassium carbonate (4.88 g, 35.31 mmol, 2.0 equiv) in 1,4-dioxane (50 mL) and water (10 mL) was added 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (1.44 g, 1.77 mmol, 0.1 equiv), and the reaction mixture was stirred under an atmosphere of N2 at 80 C for 12 h. The reaction mixture was diluted with water (100 mL) and extracted with ethyl acetate (3 x 100 mL), the combined organic phase was then washed with a sat. aqueous NaCl solution, dried over Na2SO4and concentrated. The crude product was purified by silica gel chromatography eluting with a gradient of petroleum ether : ethyl acetate (100 : 0 to 90 : 10) to give the title compound as a colorless solid (2.4 g, 54 %).1H NMR (400 MHz, CDCl3): δ = 8.83 (s, 2H), 7.01 (d, J = 1.8 Hz, 1H), 6.41 (s, 1H).

Reference： [1]Patent: WO2022/49134,2022,A1 .Location in patent: Page/Page column 205-206

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P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 32779-37-6 ] {[proInfo.proName]}

Quality Control of [ 32779-37-6 ]

Related Doc. of [ 32779-37-6 ]

Product Details of [ 32779-37-6 ]

Calculated chemistry of [ 32779-37-6 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 32779-37-6 ]

Application In Synthesis of [ 32779-37-6 ]

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

[ 32779-37-6 ] Synthesis Path-Downstream 1~61

Related Functional Groups of [ 32779-37-6 ]

Bromides

Related Parent Nucleus of [ 32779-37-6 ]

Pyrimidines

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 32779-37-6 ]

Related Parent Nucleus of
[ 32779-37-6 ]