* 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.
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[4] Journal of Physical Organic Chemistry, 2006, vol. 19, # 5, p. 295 - 307
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[ 1122-62-9 ]
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[ 1122-62-9 ]
[ 6831-82-9 ]
[ 103-74-2 ]
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[ 1122-62-9 ]
[ 4964-71-0 ]
[ 7661-55-4 ]
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[3] Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 18, p. 5464 - 5468
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[ 30235-26-8 ]
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[2] PLoS ONE, 2016, vol. 11, # 5,
[3] Journal of the Chinese Chemical Society, 2017, vol. 64, # 12, p. 1408 - 1416
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[ 1122-62-9 ]
[ 105-58-8 ]
[ 26510-52-1 ]
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[2] MedChemComm, 2016, vol. 7, # 5, p. 832 - 836
[3] Arkivoc, 2014, vol. 2014, # 2, p. 135 - 149
[4] Bioorganic and Medicinal Chemistry, 2017, vol. 25, # 15, p. 3922 - 3946
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18
[ 1122-62-9 ]
[ 4637-24-5 ]
[ 66521-54-8 ]
Yield
Reaction Conditions
Operation in experiment
51%
at 90℃; for 12 h;
A solution of 4.0 g (33.0 mmol, 1.0 eq.) of 1-(pyridin-2-yl)ethan-1-one in 13.1 mL (99.1 mmol, 3.0 eq,) of DMF dimethylacetal was stirred at 90 °C for 12 h. The mixture wasallowed to cool to room temperature, and the resulting precipitate was collected by filtration. The solids were washed with 2 x 5 mL of ethyl acetate and dried under high vacuum to provide, 3.0 g (17.0 mmol, 51percent) of (E)-3 -(dimethylamino)- 1 -(pyridin-2-yl)prop-2-en- 1-one.
13 g
for 24 h; Reflux
12.1 g of 2-acetylpyridine was dissolved in 150 ml of toluene, 30 ml of DMF-DMA was added while stirring, and the mixture was heated to reflux for 24 hours, cooled to room temperature, concentrated to dryness under reduced pressure, and 150 ml of petroleum ether was added to the residue for stirring. Disperse, filter, filter cake washed with petroleum ether to give intermediate 13g, yellow crystals.
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[11] Dalton Transactions, 2012, vol. 41, # 13, p. 3684 - 3694
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[18] Patent: US4788195, 1988, A,
[19] Patent: US4281000, 1981, A,
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[21] Patent: CN103936792, 2017, B, . Location in patent: Paragraph 0093; 0094; 0095
19
[ 1122-62-9 ]
[ 4637-24-5 ]
[ 98-86-2 ]
[ 1131-80-2 ]
[ 66521-54-8 ]
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20
[ 1122-62-9 ]
[ 54123-21-6 ]
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[ 1122-62-9 ]
[ 56100-19-7 ]
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At 15 , the bromine (1.52mL, 9.72mmol) was slowly added dropwise to 2-acetyl-pyridine (3g, 2.78mmol) in 30percent HBr / HOAc (12mL), and after completion of the dropwise addition, the reaction solution at 40 under stirring 1h, then stirred at 75 1h. The reaction solution was cooled to 20 , to which was added Et2O (30mL), and stirred at this temperature for 30min, the resulting yellow precipitate was filtered, and the precipitate was washed with 10mL diethyl ether, and dried to (6.81g, 97.8percent).
95%
at 20℃; for 23 h;
Preparation 4; 2-bromo-1 -(pyridin-2-vOethanone hvdrobromide; 30percent HBr in acetic acid (100 mL) was added at RT to a stirred solution of 2- acetylpyridine (40 g, 0.33 mol) in acetic acid (100 mL). Pyridinium tribromide (116 g) was added and the resulting mixture was stirred 23 h at RT and filtered. The solid was washed with acetic acid (3 x 100 mL) and dried at 78 0C in vacuo until sublimation began, then at RT in vacuo, giving 88.0 g (95percent) of the title substance. 1H NMR (CD3OD, 400 mHz) δ 8.82 (ddd,1H, J = 0.8, 1.7, 4.6 Hz), 8.73 (id. 1H, J = 1.5, 8.0 Hz), 8.28 (ddd, 1 H, J = 1, 1, 8 Hz)1 8.14 (ddd, 1H, J = 1, 5, 8 Hz), 3.91 (A of AB, 1H, J = 11.6 Hz), 3.81 (B of AB, 1H, J = 11.6 Hz).
93%
at 0 - 70℃; for 3 h;
To a solution of 1-(pyridin-2-yl)ethan-1-one (3.0 g, 24.8 mmol) in HBr in AcOH (30 mL) at 0°C, bromine (3.9 g, 24.8mmol) was added drop wise and allowed the mixture to stir at 70°C for 3 hours. After TLCshowed completion, diluted the mixture with diethyl ether (50 mL) and filtered and washedwith diethyl ether to obtain 2-bromo-1-(pyridin-2-yl)ethan-1-one hydrobromide 3 (6.5 g, 93percentyield), as cream colored solid; 1H NMR (400 MHz, DMSO-d6): δ 5.02 (s, 2H), 7.73 (m, 1H),8.01 (m, 2H), 8.75 (d, J = 4.4 Hz, 1H). All data are consistent with literature values [17].
93%
With bromine In tetrachloromethane for 1 h; Reflux
(2-Bromoacetyl)pyridin-1-ium bromide (A): To a stuffed solution of 1-(pyridin-2- yl)ethan-1-one (2.0 g, 16.6 mmol) in Cd4 (60 ml), bromine (2.7 g, 16.60 mmol) was added dropwise. After complete addition the final reaction mixture was refluxed for 1 h. The precipitate was collected by filtration and washed 2-3 times with diethylether and dried to obtain compound A as a beige solid (2.94 g, 93percent).
87%
With hydrogen bromide; pyridinium hydrobromide perbromide In acetic acid at 40℃;
EXAMPLES The following Examples are intended to illustrate the scope of the present invention and should not be considered to limit it in any way. (A) Preparation of the intermediates of the formula (III EXAMPLE NO. 1 A) Synthesis of 2-bromoacetyl-pyridine hvdrobromide 100 g of 2-acetylpyridine were dissolved in 366 ml of 33percent hydrobromic acid in acetic acid; the solution was heated to 40°C and a solution of 264 g of pyridinium tribromide in 500 ml of acetic acid was added. The mixture was kept at 40°C overnight. The reaction mixture was cooled and the precipitate filtered out and washed with 200 ml of acetic acid. The precipitate was resuspended in 400 ml of THF, then filtered out and dried, giving rise to 200 g of 2-bromoacetyl-pyridine hydrobromide (yield 87percent).
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[17] Patent: WO2009/114552, 2009, A1, . Location in patent: Page/Page column 112
27
[ 1122-62-9 ]
[ 562-10-7 ]
Reference:
[1] Patent: CN103524403, 2016, B,
28
[ 1122-62-9 ]
[ 616-38-6 ]
[ 75418-74-5 ]
Yield
Reaction Conditions
Operation in experiment
51%
Stage #1: With sodium hydride In cyclohexane for 0.166667 h; Heating / reflux Stage #2: at 20℃; Heating / reflux Stage #3: With water; acetic acid In cyclohexane at 0℃;
Step 2: Preparation of Methyl 3-oxo-3-pyridin-2-ylpropanoate; NaH (60percent suspension on mineral oil; 30g, 750 mmol, 2.5 equiv.) was suspended in cyclohexane (900 mL) and the temperature raised to reflux. To this mixture was added 2-acetyl pyridine (36 g, 300 mmol) dropwise, followed, after 10 min, by dimethyl carbonate (100 mL, 1.2 mol, 4 equiv.). The reaction mixture was heated at reflux for 4 h, stood at room temperature overnight and then cooled to 0° C. The near solid mixture was quenched by addition of AcOH (75 mL) in H2O (250 mL), then diluted with Et2O (250 mL) and stirred until all solids had dissolved. The aqueous layer was separated and extracted with Et2O (2.x.), the combined organic extracts dried (MgSO4) and concentrated under reduced pressure. The crude orange oil was distilled to give recovered 2-acetyl pyridine (40° C./0.3 mbar; 6.5 g, 18percent) and product (105° C./0.6 mbar; 27.5 g, 51percent).
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[1] Patent: US2008/161254, 2008, A1, . Location in patent: Page/Page column 14
[2] Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 2, p. 836 - 851
[3] Chemical Communications, 2012, vol. 48, # 17, p. 2340 - 2342
[4] Tetrahedron Letters, 2014, vol. 55, # 48, p. 6534 - 6537
[5] Organic Letters, 2014, vol. 16, # 20, p. 5410 - 5413
[6] Advanced Synthesis and Catalysis, 2016, vol. 358, # 13, p. 2035 - 2040
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[3] Organic and Biomolecular Chemistry, 2016, vol. 14, # 15, p. 3793 - 3808
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[15] Supramolecular Chemistry, 2018, vol. 30, # 8, p. 706 - 712
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[ 112881-51-3 ]
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[2] New Journal of Chemistry, 2016, vol. 40, # 7, p. 5775 - 5781
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[ 1122-62-9 ]
[ 27854-90-6 ]
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[ 1122-62-9 ]
[ 87227-77-8 ]
[ 109-97-7 ]
[ 27854-90-6 ]
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[1] Advanced Synthesis and Catalysis, 2016, vol. 358, # 10, p. 1618 - 1624
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[ 1122-62-9 ]
[ 110-60-1 ]
[ 5724-81-2 ]
[ 27854-90-6 ]
[ 27854-90-6 ]
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[ 1122-62-9 ]
[ 27854-90-6 ]
[ 27854-90-6 ]
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[1] Patent: US2008/207573, 2008, A1,
37
[ 1122-62-9 ]
[ 4637-24-5 ]
[ 75415-03-1 ]
Yield
Reaction Conditions
Operation in experiment
30%
Stage #1: at 100℃; for 16 h; Reflux Stage #2: With hydrazine hydrate In ethanol at 60℃; for 0.5 h;
A mixture of N-dimethoxymethyl-N,N-dimethylamine(10 mL) and 2-acetylpyridine (40 mL) was refluxed at 100 °C for 16 h, then concentrated by rotating evaporationto give dark brown solid. This was washed with hexane(100 mL) and diethyl ether (100 mL) to give the pure and bright yellow crystalline product. Hydrazine monohydrate (40 mL) and ethanol (15 mL) were mixed with the previously obtained solid, and the mixture was stirred at 60 °C for 30 min. After cooling, distilled water (75 mL) was added to the solution, which was kept at 0 °C for 24 h to produce a light yellow precipitate. This was recrystallized from a mixture of dichloromethane and hexane.
Reference:
[1] Transition Metal Chemistry, 2018, vol. 43, # 3, p. 211 - 220
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[ 1122-62-9 ]
[ 75415-03-1 ]
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[12] European Journal of Inorganic Chemistry, 2017, vol. 2017, # 3, p. 651 - 658
39
[ 1122-62-9 ]
[ 123-11-5 ]
[ 13104-56-8 ]
Yield
Reaction Conditions
Operation in experiment
45.62%
Stage #1: With potassium hydroxide In ethanol at 20℃; for 0.166667 h; Stage #2: With ammonium hydroxide In ethanol at 37℃; for 24 h;
General procedure: Synthesis of 4′-(3-methoxyphenyl)-2,2′:6′,2″-terpyridine (3-MeO-Phtpy), 4′-(2-methoxyphenyl)-2,2′:6′,2″-terpyridine (2-MeO-Phtpy) and 4′-(4-methoxyphenyl)-2,2′:6′,2″-terpyridine (4-MeO-Phtpy) were performed using the methods described previously [27–33]. 2-Acetylpyridine (2.813g, 23.2mmol, 2 eq.) was added to 2-methoxybenzaldehyde, 3-methoxybenzaldehyde or 4-methoxybenzaldehyde (11.6mmol, 1 eq.) dissolved in 50mL ethanol. KOH pellets (46.5mmol, 4 eq.) were added to this solution. The reaction mixture was stirred at room temperature for 10min. NH3 (40mL, 25percent aq.) was slowly added to the reaction mixture. After a 24-h incubation at 37°C, 5mL of 25percent aq. NH3 was added to the reaction mixture again. The flask containing the reaction mixture was cooled to−20°C. The obtained white precipitate in the flask was isolated through filtration and washed with cold ethanol. We further purified the each product using recrystallization in ethanol-H2O. After recrystallization, each product was recovered by filtration, washed with cold ethanol and petroleum ether, and dried under high vacuum for 24h (Scheme 1).
37%
With ammonium hydroxide; potassium hydroxide In ethanol at 20℃; for 24 h;
General procedure: Ketone (20 mmol) (2-acetylpyridine, 2-acetylthiazole or 2-acetylpyrazine)was added to a solution of aldehyde (10 mmol) (4-methoxybenzaldehyde,4-methoxy-1-naphthaldehyde or 6-methoxy-2-naphthaldehyde) in EtOH (75 mL). KOH (1.54 g, 27.5 mmol) and NH3(aq)(35 mL) were then added. The solution was stirred at room temp. for 24 h. The solid was collected by filtration and washed with H2O. Recrystallization from ethanol (L1,L4, L7) or toluene (L2, L3, L5, L6, L8,L9) afforded a crystalline solid. 4′-(4-methoxy-1-phenyl)-2,2′:6′,2″-terpyridine (L1): Yield: 37percent. IR(KBr, cm−1): 1588(s), 1467(m), 1389(m), 1204(m), 1157(m),1069(m), 790(m), 739(m) and 655(m). NMR: 1H NMR (400 MHz,CDCl3) δ 8.73 (d, J=4.1 Hz, 2H, HA1), 8.71 (s, 2H, HB2), 8.67 (d,J=7.9 Hz, 2H, HA4), 7.90–7.85 (m, 4H, HC2+A3), 7.37–7.33 (m, 2H,HA2), 7.03 (d, J=8.7 Hz, 2H, HC3), 3.88 (s, 3H, HC5). 13C NMR(100 MHz, CDCl3) δ 160.66, 156.55, 155.99, 149.90, 149.24, 136.96,130.92, 128.67, 123.87, 121.49, 118.42, 114.46, 55.52. C22H17N3O(339.39 g mol−1): calcd C, 77.86; H, 5.05; N, 12.38percent; found: C, 77.46;H, 5.35; N, 12.25percent. DSC: (I run) Tm=164 °C; (II run) Tg=30, Tc=82and Tm=163 °C.
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[ 1122-62-9 ]
[ 13104-56-8 ]
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43
[ 1122-62-9 ]
[ 556-18-3 ]
[ 178265-65-1 ]
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44
[ 1122-62-9 ]
[ 148332-36-9 ]
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[1] European Journal of Inorganic Chemistry, 2017, vol. 2017, # 12, p. 1667 - 1672
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45
[ 1122-62-9 ]
[ 1571-08-0 ]
[ 158014-74-5 ]
Yield
Reaction Conditions
Operation in experiment
50%
With ammonia; sodium hydroxide In ethanol; water at 20℃; for 17 h;
Round bottom flask 4-methoxycarbonyl benzaldehyde (1.0g, 6.1mmol) and 2-acetyl pyridine (1.37ml, 12.2mmol) were dissolved in 25ml of ethanol.Then 30percent NH3were placed in a round flask, that the solution (1ml) and NaOH (0.488g, 12.2mmol) was dissolved in a minimal amount of water.Put the clear liquid solution of NaOH runners ttuieotgo is light yellow, and after about an hour and caught the red.In about 17 hours at room temperature, open the entrance to the round bottom flask and stirred haenotgo allow air to enter.Over time, the precipitate produced was more yellow.After the reaction was terminated, and then dissolved into water (50ml) and neutralized with HCl.The precipitate was filtered out and washed with water by filtration.And placed in 50ml of ethanol was refluxed for 1 hour and filtered and dried under vacuum (yield: 50percent).
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[1] Inorganic Chemistry, 2017, vol. 56, # 22, p. 13679 - 13696
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[ 1122-62-9 ]
[ 158014-74-5 ]
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[ 1122-62-9 ]
[ 159307-02-5 ]
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[1] Angewandte Chemie - International Edition, 2017, vol. 56, # 36, p. 10890 - 10893[2] Angew. Chem., 2017, vol. 129, p. 11030 - 11033,4
With ammonia; potassium hydroxide; In ethanol; at 20℃;
General procedure: The one-pot preparation method of Krohnke type 4'-aryl-2,2':6',2''-terpyridine ligands was performed to obtainligands L1-L5 according to the literature [23] with aslight modification. 2-Acetylpyridine (0.56 cm3,5.0 mmol) was added to a solution of 0.25 cm3 benzaldehyde(2.5 mmol) in 18 cm3 ethanol. After addition of the mixture of 0.280 g KOH (5.0 mmol) and 0.5 cm3 NH3(25 %, 6.5 mmol), the solution was stirred overnight at room temperature, during which time as orange suspension was appeared. The solid was collected by filtration and washed with EtOH (3 9 6 cm3). Then, the crude solid product was recrystallized by cooling the hot super saturated ethanolic solution. The preparation method of diketone ligand (L6) was performed similar to the above procedure for the preparation of substituted phenyl terpyridines without the addition of ammonia. The prepared ligand was characterized in good agreement with the literature [24].
With ammonium acetate; sodium hydroxide; In ethanol; water;
L2 was prepared by a similar method as described for L1, except for using of pyridine-4-carbaldehyde instead of pyridine- 3-carbaldehyde.
Sodium hydride (2.9 g, 124 mmmol) was taken in dry THF (50 mL) in a 100 mL round bottom flask under N2 and cooled it down to 0 C. To it was added a solution of 1-(pyridin-2-yl)ethan-1-one (5.0 g, 41.3 mmol) in THF (5 mL). The reaction mixture was stirred at rt for 30 min followed by the addition of diethyl carbonate (20 mL, 165 mmol). The reaction mixture was then stirred at rt for 12 h. Ice-cooled water was added dropwise to quench the reaction. It was extracted with EtOAc (3 * 100 mL). The combined organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude was further triturated with diethyl ether which afforded 26 as a pale yellow semi-solid (4.0 g, 50%). LCMS(ESI) m/z 194.06 [M+H+]; 40% (purity).
With ammonia; sodium hydroxide; In ethanol; water; at 20℃; for 17h;
Round bottom flask 4-methoxycarbonyl benzaldehyde (1.0g, 6.1mmol) and 2-acetyl pyridine (1.37ml, 12.2mmol) were dissolved in 25ml of ethanol.Then 30% NH3were placed in a round flask, that the solution (1ml) and NaOH (0.488g, 12.2mmol) was dissolved in a minimal amount of water.Put the clear liquid solution of NaOH runners ttuieotgo is light yellow, and after about an hour and caught the red.In about 17 hours at room temperature, open the entrance to the round bottom flask and stirred haenotgo allow air to enter.Over time, the precipitate produced was more yellow.After the reaction was terminated, and then dissolved into water (50ml) and neutralized with HCl.The precipitate was filtered out and washed with water by filtration.And placed in 50ml of ethanol was refluxed for 1 hour and filtered and dried under vacuum (yield: 50%).
Method A 51 ml of dimethyl carbonate was added to a mixture of 30 g of pentane-washed sodium hydride in 150 ml of benzene and the mixture was stirred and heated at reflux for 30 minutes. Then a solution of 36 g of 2-acetylpyridine in 50 ml of benzene was added dropwise over 1 hour. 150 ml of THF was added to facilitate stirring, the mixture was stirred and heated for a further 1 hour, and cooled to room temperature. A mixture of 250 ml of water and 75 ml of glacial acetic acid was added dropwise while the mixture was cooled to hold its temperature to about 15 C. Two liquid liquid layers formed; the upper layer was separated, dried (Na2 SO4) and stripped of solvents. The residue was distilled in a Kugelrohr apparatus at 110-115 C./0.05 Torr., to give methyl 3-(2-pyridinyl)-3-oxopropanoate (7A), as a yellow oil.
73 ml of diethyl carbonate was added to a mixture of 30 g of hexane-washed sodium hydride and 150 ml of benzene, and the resulting mixture was heated at reflux temperature for 30 minutes, when 33 ml of 2-acetylpyridine was added dropwise over 60 minutes. The mixture was cooled to room temperature, 75 ml of glacial acetic acid and 250 ml of water were added, and the mixture was extracted with diethyl ether. The extract was dried, stripped of solvent and the residue was distilled in a Kugelrohr apparatus to give 6A.
To 8 g of compound 130 in 30 mL of methanol. 11.8 ml of thionyl chloride was added slowly at 5 C. The mixture was allowed to stir for 30 min at room temperature, and was refluxed overnight. The reaction mixture was concentrated under high vacuum, then dissolve in sodium bicarbonate solution. Then compound was extracted into dichloromethane, then dried and concentrated to give a 70% yield of compound 131. To 6 g of compound 131 in 100 mL benzene, 2.6 g of NaOMe was added. The reaction mass was heated to 80 C. and 5 ml of ethyl acetate was added to the reaction and further refluxed for an additional one hour. The reaction was neutralized with citric acid and extracted with dichloromethane. Removal of solvent afforded a 60% yield of compound 132. To 4 g of compound 132 was added 40 mL of 20% sulphuric acid, which was then refluxed for two hours. Then reaction mixture was neutralized with the sodium hydroxide, extracted into dichloromethane, and concentrated to give a yield of 60% of desired compound 133. To a 1 liter round bottom flask with 150 mL of DMF was added compound 133 added at 0 C. To the reaction mixture was added hydrogen peroxide and ferrous sulphate heptahydrate simultaneously at 0 C. The reaction mixture was allowed to stir overnight. The reaction mixture was poured in the water, then extracted with dichloromethane. The organic layer was dried over sodium sulphate and concentrated to afford 2% of desired compound 134. To 1 g of compound 134 in 10 mL benzene was added 0.8 g of sodium methoxide. The reaction mixture was heated gently to reflux, and allowed to stir for two hours. The reaction mixture was neutralized with citric acid then extracted with ethyl acetate. The organic layer was dried and concentrated to give 80% yield of the compound 135. To 200 mg of compound 135 in ethanol was added methyl hydrazine. The mixture was allowed to stir for six hours at room temperature. Then reaction mixture was neutralized with sodium bicarbonate and extracted with ethyl acetate. The organic layer was then dried and concentrated to afford a 50% yield of the final compound 136.
Step 2: Preparation of Methyl 3-oxo-3-pyridin-2-ylpropanoate; NaH (60% suspension on mineral oil; 30g, 750 mmol, 2.5 equiv.) was suspended in cyclohexane (900 mL) and the temperature raised to reflux. To this mixture was added 2-acetyl pyridine (36 g, 300 mmol) dropwise, followed, after 10 min, by dimethyl carbonate (100 mL, 1.2 mol, 4 equiv.). The reaction mixture was heated at reflux for 4 h, stood at room temperature overnight and then cooled to 0 C. The near solid mixture was quenched by addition of AcOH (75 mL) in H2O (250 mL), then diluted with Et2O (250 mL) and stirred until all solids had dissolved. The aqueous layer was separated and extracted with Et2O (2×), the combined organic extracts dried (MgSO4) and concentrated under reduced pressure. The crude orange oil was distilled to give recovered 2-acetyl pyridine (40 C./0.3 mbar; 6.5 g, 18%) and product (105 C./0.6 mbar; 27.5 g, 51%).
(E)-2-[N'-(1-pyridin-2-yl-ethylidene)hydrazino]acetatocopper[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58.8%
In water; acetonitrile; at 39.84℃; for 0.5h;Reflux;
The solution of haOEt·HCl (0.15 g, 1.0 mM) and ap (0.12 g, 1.0 mM) in a MeCN/H2O mixture (20 mL/5 mL) was heated with stirring until the temperature reached 313 K, followed by addition of CuCl2·2H2O (0.16 g, 0.94 mM). The reaction mixture was refluxed for 30 min and cooled to ambient temperature. Green crystals of 1 were obtained from the mother liquor, filtered off and washed with ether. Yield: 0.19 g (58.8%). Anal. Calcd for C9H10ClCuN3O2 (%): C, 37.12; H, 3.46; N, 14.43. Found: C, 36.91; H, 3.67; N, 14.47. IR (ATR, cm-1): 3243 (m), nu(N-H); 1610 (vs. br), nuas(COO) and nu(C=N); 1374 (s), nus(COO); 1023 (m), nu(N-N); 650 (w), (pyridine, in plane); 478 (w), (pyridine, out of plane). LambdaM (1*10-3 M, DMF): 19.5 Omega-1*cm2*M-1. mu (304 K) = 1.91 muB. ESI-MS: [M-Cl+DMSO]+ (C11H16N3O3SCu) Calcd m/z 333.0208, found 333.0216.
bis((E)-2-[N'-(1-pyridin-2-yl-ethylidene)hydrazino]acetato)dizinc[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68.2%
In ethanol; for 1h;Reflux;
A warm solution of ap (0.12 g, 1.0 mM) and haOEt·HCl (0.15 g, 1.0 mM) in absolute ethanol(10 mL) was added to a warm solution of Zn(AcO)2·2H2O (0.22 g, 1.0 mM) in absolute ethanol (10mL). The reaction mixture was refluxed for 1 h and cooled to ambient temperature. After two days white crystals of 2 formed were filtered from the mother liquor and washed with ether. Yield 0.20 g (68.2%). Anal. Calcd for C18H20Cl2N6O4Zn2(%): C, 36.89; H, 3.44; N, 14.34. Found: C, 36.81; H, 3.41; N, 14.35. IR (ATR, cm-1):3235 (m), nu(N-H); 1646 (vs), nuas(COO) and nu(C=N); 1372 (s), nus(COO); 670 (w), (pyridine,in plane); 490 (w), (pyridine, out of plane). 1H NMR (500 MHz, DMSO-d6): delta = 2.23(s, 3H, H-C9), 3.73 (d, 2H, H-C7), 7.55 (br t, 1H, H-N3), 7.84 (d, 1H, H-C3), 8.10(ovlp, m, 2H, H-C4, and H-C5), 8.49 (br, m, 1H, H-C6). 13C NMR (125.8 MHz, DMSO-d6): delta = 11.3 (C9), 53.0 (C7), 121.1 (C3), 124.6 (C5), 137.0 (C4), 141.1 (C6), 148.8 (C2),150.0 (C1), 173.1 (C8). LambdaM (1*10-3 M, H2O): 55.2 Omega-1*cm2*M-1. IR and NMR spectroscopic data, as well as molar conductivity measurements are in agreement with the data previously published [8].
6-chloro-4-(2-fluorophenyl)-2-(pyridin-2-yl)quinoline[ No CAS ]
(5E, 11E)-2,8-dichloro-6,12-bis(2-fluorophenyl)dibenzo[b,f][1,5]diazocine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64.1%; 13%
With diphenyl hydrogen phosphate; for 0.05h;Microwave irradiation;
General procedure: 2-Aminobenzophenone 1 (1 mmol), heteroaromatic ketone 2 (1 mmol), and diphenylphosphate (DPP) (0.5 mmol) were mixed without any organic solvent and the reaction mixture was irradiated in the microwave oven(RE-555 TCW, Samsung, Busan, Korea) for 3 min. Resulting reaction mixture was diluted with 50 mL of ethyl acetate, neutralized with aqueous 10% NaOH and extracted with ethylacetate three times, washed with water, and dried using MgSO4. Products were purified by column chromatography (ethyl acetate/n-hexane = 1/20-1/40 v/v) to give the corresponding quinoline compounds 3-7. (Analytical data provided in Supporting Information).
2-Quinterpy was synthesised by slight adjustment of a reported procedure [8] adopted from the Kroehnke approach. Sodium hydroxide (0.361g, 9.03mmol) was dissolved in a solution of water (10ml) and ethanol (10ml) then cooled to 0C. 2-Acetylpyridine, (0.5ml, 4.46mmol) was then added by use of a syringe then stirred at 0C for 30min. This was followed by the addition of a chilled solution at (0C) of isoquinolinecarboxaldehyde (0.351g, 2.23mmol) in 20ml ethanol and stirred for 6h while maintaining the temperature at 0C. The reaction mixture was then allowed to warm up to ambient temperature and thereafter a 25% aqueous ammonia solution (30ml) was added and stirred for a further 18h resulting in the formation of a white precipitate. Water (10ml) was added to the reaction mixture followed by filtration of the precipitate which was rinsed with 50ml of water and then with 20ml of a 1:1 water:ethanol solution. The resulting white solid was dried under vacuum. Yield 0.578g, 72%. Melting point: 458.15K, 1H NMR (400mHz, DMSO-d6 25C): delta=7.51 (ddd, 3JH,H=7.4Hz, 3JH,H=4.6Hz, 4JH,H=1.0Hz, 2H, Hb-Py), 7.67 (t, 3JH,H=14.1Hz, 3JH,H=7.1Hz, 1H, Hj-Quin), 7.84 (t, 3JH,H=16.6Hz, 3JH,H=8.3Hz, 1H, Hi-Quin), 8.02 (td, 3JH,H=7.7Hz, 3JH,H=1.7Hz, 2H, Hc-Py), 8.05 (d, 3JH,H=7.5Hz, 1H, Hf-Quin), 8.20 (d, 3JH,H=8.2Hz, 1H, Hh-Quin), 8.29 (d, 3JH,H=8.6Hz, 1H, Hk-Quin), 8.55 (d, 3JH,H=8.6Hz, 1H, Hg-Quin), 8.65 (d, 3JH,H=7.9Hz, 2H, Ha-Py), 8.78 (dt, 3JH,H=4.1Hz, 3JH,H=0.7Hz, 2H, Hd-Py), 9.18 (s, 2 He-Py) ppm. 13C NMR (400MHz, DMSO-d6 25C): delta=118.13 (C11-Quin), 118.82 (C7-Py), 120.91 (C4-Py), 124.52 (C2-Py), 127.35 (C16-Quin), 127.74 (C12-Quin), 127.90 (C14-Quin), 129.33 (C15-Quin), 130.35 (C13-Quin), 137.42(C17-Quin), 137.85 (C3-Py), 147.51 (C10-Quin), 147.91 (C1-Py), 149.29 (C8-Py), 153.75 (C5-Py), 154.84 (C6-Py), 155.76 (C9-Quin) ppm. UV/Vis (acetonitrile) lambdamax: 205, 255, 312nm. Elemental analysis Calcd for C24H16N4: C, 79.98; H, 4.47; N, 15.55. Found; C, 79.99; H, 4.30; N, 15.50. MS (TOF): m/z (%): Calcd. For [M-Na]+; 383.1273. Found: 383.1275 (100) [M-Na]+, 383.1308 (30%) [L-Na]+
4′-(6-methoxy-2-naphthyl)-2,2′:6′,2″-terpyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
42%
With ammonium hydroxide; potassium hydroxide; In ethanol; at 20℃; for 24h;
General procedure: Ketone (20 mmol) (2-acetylpyridine, 2-acetylthiazole or 2-acetylpyrazine)was added to a solution of aldehyde (10 mmol) (4-methoxybenzaldehyde,4-methoxy-1-naphthaldehyde or 6-methoxy-2-naphthaldehyde) in EtOH (75 mL). KOH (1.54 g, 27.5 mmol) and NH3(aq)(35 mL) were then added. The solution was stirred at room temp. for 24 h. The solid was collected by filtration and washed with H2O. Recrystallization from ethanol (L1,L4, L7) or toluene (L2, L3, L5, L6, L8,L9) afforded a crystalline solid.
With potassium hydroxide; In ethanol; at 70℃; for 3h;
In a 1 L three-neck flask10 g (50 mmol) of <strong>[59278-65-8]2-amino-4-bromobenzaldehyde</strong> and 6.06 g (50 mmol) of 2-acetylpyridine were added thereto. 100 ml of ethanol was added to dissolve the material, and a solution of 2.81 g (50 mmol) of KOH was slowly added to 50 ml of ethanol. It stirred at 70 degreeC for 3 hours. After the reaction was completed, the mixture was cooled, filtered, and the solid was washed with H 2 O and purified by column chromatography to obtain 12 g of intermediate D (85.7%).