* 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.
Reference：
[1] Journal of the American Chemical Society, 2006, vol. 128, # 39, p. 12714 - 12725
4
[ 623-27-8 ]
[ 26104-68-7 ]
[ 13001-40-6 ]
Reference：
[1] Journal of Pharmaceutical Sciences, 1982, vol. 71, # 4, p. 465 - 466
5
[ 623-27-8 ]
[ 104-85-8 ]
[ 13001-40-6 ]
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1986, vol. 25, p. 485 - 488
6
[ 623-27-8 ]
[ 651-12-7 ]
Reference：
[1] Journal of Organic Chemistry, 1993, vol. 58, # 7, p. 1827 - 1830
[2] Tetrahedron, 1964, vol. 20, p. 1625 - 1632
7
[ 23973-65-1 ]
[ 623-27-8 ]
[ 13001-39-3 ]
Yield
Reaction Conditions
Operation in experiment
91%
With sodium methylate In methanol; N,N-dimethyl-formamide at 35℃; for 3 h; Green chemistry
Under atmospheric pressure, 498.6 g of triethyl phosphite and 1000 ml of p-xylene were charged into a closed reactor equipped with a reflux condenser, heated to 140 ° C, and 151.6 g of an o-cyanobenzyl chloride solution (The molar ratio of triethyl phosphite and o-cyanobenzyl chloride is 3: 1), the feeding time is 2h, after the reaction is kept for 10h after completion of the reaction, the excess triethyl phosphite and the reaction solvent are recovered by distillation and reused; The resulting reaction mixture was cooled to 25-30 ° C, dissolved in 500 ml of N, N-dimethylformamide (DMF), dissolved in equimolar amounts for 3 hours under stirring, and 67 g of terephthalic aldehyde and 180 g of 30percent Sodium methoxide methanol solution, the temperature dropped to 35 ° C after the end of the incubation reaction 3h, then cooled to 30 ° C, adjust the PH value to 7, cooled to 10 ~ 15 ° C, centrifuged, the resulting crude product was refined methanol , Finely centrifuged, and the crude product was centrifuged and dried to obtain 1,4-bis (o-cyanostyryl) benzene. The yield was 92percent and the purity was 98percent. The mother liquor was distilled to remove DMF and methanol [DMF back to the condensation process, methanol to refined crude], to give two phosphate Ethyl ester, yield 91percent, purity 96percent.
Reference：
[1] Patent: CN107673998, 2018, A, . Location in patent: Paragraph 3; 6; 7; 8
8
[ 529-19-1 ]
[ 623-27-8 ]
[ 13001-39-3 ]
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1986, vol. 25, p. 485 - 488
9
[ 623-27-8 ]
[ 51359-78-5 ]
Reference：
[1] Russian Chemical Bulletin, 2004, vol. 53, # 9, p. 2080 - 2085
[2] Journal of the American Chemical Society, 2005, vol. 127, # 3, p. 818 - 819
[3] Journal of the American Chemical Society, 1996, vol. 118, # 8, p. 1841 - 1855
[4] Chemical Communications, 2013, vol. 49, # 94, p. 11041 - 11043
[5] Molecules, 2016, vol. 21, # 7,
[6] Organic Letters, 2017, vol. 19, # 24, p. 6756 - 6759
[7] Patent: CN107522654, 2017, A,
[8] Patent: CN107522647, 2017, A,
10
[ 589-29-7 ]
[ 623-27-8 ]
[ 52010-97-6 ]
[ 51359-78-5 ]
Reference：
[1] Patent: US4733012, 1988, A,
11
[ 623-27-8 ]
[ 63525-48-4 ]
Reference：
[1] Chemistry - An Asian Journal, 2018, vol. 13, # 18, p. 2691 - 2699
12
[ 623-27-8 ]
[ 19675-63-9 ]
Reference：
[1] Chemische Berichte, 1912, vol. 45, p. 1586
[2] Chemische Berichte, 1912, vol. 45, p. 1586
[3] Justus Liebigs Annalen der Chemie, 1885, vol. 231, p. 363
13
[ 623-27-8 ]
[ 122-51-0 ]
[ 81172-89-6 ]
Yield
Reaction Conditions
Operation in experiment
50%
With ammonium chloride In ethanol at 0 - 20℃;
A mixture of terephthalaldehyde (10 g, 74.55 mmol), ammonium chloride (160 mg, 3.0 mmol) in ethanol (10.3 g, 223.6 mmol) was added dropwise triethoxymethane (12.15 g, 82 mmol) at 0° C. After the addition, the mixture was stirred at room temperature overnight. The mixture was concentrated, the residue was purified by silica gel chromatography to give the title compound (7.0 g, yield 50percent) as a white solid. LC-MS (ESI) m/z: 209 (M+1)+
50%
With ammonium chloride In ethanol at 0 - 20℃;
Example 125 A4-(Diethoxymethyl)benzaldehyde[00764] A mixture of terephthalaldehyde (10 g, 74.55 mmol), ammonium chloride (160 mg, 3.0 mmol) in ethanol (10.3 g, 223.6 mmol) was added dropwise triethoxymethane (12.15 g, 82 mmol) at 0 °C. After the addition, the mixture was stirred at room temperature overnight. The mixture was concentrated, the residue was purified by silica gel chromatography to give the title compound (7.0 g, yield 50percent) as a white solid. LC-MS (ESI) m/z: 209 (M+l)+.
Reference：
[1] Patent: US2010/35883, 2010, A1, . Location in patent: Page/Page column 91
[2] Patent: WO2011/130661, 2011, A1, . Location in patent: Page/Page column 178
[3] Journal of Enzyme Inhibition and Medicinal Chemistry, 2019, vol. 34, # 1, p. 204 - 218
To a solution of terephthalaldehyde (5 g, 36.54 mmol) in tetrahydrofuran (THF) methyl (triphenylphosphoranylidene)acetate (13.09 g, 38.37 mmol) was added at room temperature. The solution was stirred at room temperature for 4 hours. The resulting solution was washed with water three times and the organic layer was collected. The residue was purified via chromatography eluted with ethyl acetare and hexane to provide a solid (6.17 g, 89 %). H NMR (300 MHz, DMSO-rfe): delta 3.74 (s, 3H, OCH3), 6.81 (d, 1H, / = 16.2 Hz, CH=CH), 7.73 (d, 1Eta, J = 16.2 Hz, CH=CH), 7.90-7.97 (m, 4Eta, ArH), 10.02 (brs, 1Eta, CHO).
(E)-4-(2-(benzo[d]oxazol-2-yl)vinyl)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
With potassium tert-butylate; In tetrahydrofuran; methanol; THF-1N HCl; THF-t-BuOH; water;
25 p-[trans-2-(benzoxazol-2-yl)ethenyl]benzaldehyde STR19 To a solution of terephthaldehyde momo (diethyl acetal) 21 (5.000 g, 24 mmol.), 2-methylbenzoxazole in 5:1 THF-t-BuOH (77.4 mL) cooled at -5° C., was added t-BuOK in THF (1.0M, 36.0 mL, 36.0 mmol.) in such a rate to keep the internal temperature of the reaction below 0° C. (ca. 10 min). The resulting mixture was stirred under nitrogen overnight during which time the temperature rised up to room tempt. It was then diluted with ethyl acetate and washed with sat. sodium bicarbonate. The organic layer was dried (Na2 SO4) and evaporated to give a brown oily solid. It was then dissolved in boiling methanol (50 mL) and cooled to room tempt. The white solid was precipitated out after the addition of water (25 mL) and the solid was collectted. The acetal thus obtained was hydrolyzed by stirring the product in 3:1 THF-1N HCl solution for 10 min. The mixture was extracted with ethyl acetate, the organic layers were washed with sat. sodium bicarbonate, brine and dried (Na2 SO4). Evaporation gave a slightly yellow solid 25, 4.43 g (74percent overall yield). Compound 25 has: 1 H NMR (400 MHz, CDCl3) delta7.14 (d, 1 H), 7.31 (m, 2 H), 7.49 (m, 1 H), 7.68 (m, 3 H), 7.75 (d, 1 H), 7.86 (d, 2 H), 10.00 (s, 1 H).
To an oven dried 50ml round bottomed flask was added terephthalaldehyde (0.200g, 1. 49mmol) and methyl-4-amino-3-hydroxy-benzoate (0.498g, 2. 98mmol). Ethanol (15ml) was added and the reaction mixture heated to 55C for 5 hours under a nitrogen atmosphere. The precipitate which forms was filtered through a sinter funnel and washed with ethanol (40ml). The precipitate, the product WSP714, was isolated as a yellow powder and dried under high vacuum. No further purification was necessary. Yield 0. 491g (1. 13mmol, 76%); mp 263-266C ; 1H NMR (300MHz, d6-DMSO) 6 3. 84 (6H, s, Cl-H), 7.26 (2H, d, J = 8. 1Hz, C7-H), 7.50 (4H, m, C4-H + Cg-H), 8.16 (4H, s, Cii- H), 8.78 (2H, s, Cg-H), 9.68 (2H, br, s, OH); 13C NMR (75MHz, d6-DMSO) 6 52.4 (Cl), 116.9 (C4), 120.4 (C7), 121.1 (C8), 128. 3 (C11), 129.6 (C3), 138.9 (Clo), 143.1 (C6), 150.9 (C5), 161.6 (C9), 166.2 (C2); (Anal. Calcd. for C24H2oN206 + 0.1H2O : C, 66. 38 ; H, 4.69 ; N, 6.45%. Found C, 66.25 ; H, 4.36 ; N, 6.26%).
[0096] 25 mg (0.1058 mmol) <strong>[298-46-4]carbamazepin</strong>e and 7 mg (0.0521 mmol) p-phthalaldehyde were dissolved in approximately 3 mL methanol. Slow evaporation of the solvent yielded colorless needles of a 1:1 <strong>[298-46-4]carbamazepin</strong>e/p-phthalaldehyde co-crystal, as shown in FIG. 10B. [0097] Crystal data: (Bruker SMART-APEX CCD Diffractometer), C38H30N4O4, M=606.66, monoclinic C2/c; a=29.191(16), b=4.962(3), c=20.316(11) , beta=92.105(8), U=2941(3) 3, T=200(2) K, Z=4, mu(Mo-Kalpha)=0.090 mm, Dc=1.370 Mg/m3, lambda=0.71073 3, F(OOO)=1272, 2thetamax=43.660, 3831 reflections measured, 1559 unique (Rint=0.0510). Final residuals for 268 parameters were R1=0.0332, wR2=0.0801 for I>2?(I), and R1=0.0403, wR2=0.0831 for all 1559 data. [0098] Crystal packing: The co-crystals contain hydrogen bonded carboxamide homodimers that crystallize in the space group C2/c. The 10 amines of the homodimer are bifurcated to the carbonyl of the p-phthalaldehyde forming a chain with an adjacent homodimer. The chains pack in a crinkled tape motif sustained by ?-? interactions between phenyl rings of the CBZ. [0099] Infrared Spectroscopy: (Nicolet Avatar 320 FTIR). The 10 amine unsymmetrical and symmetrical stretching was shifted down to 3418 cm-1; aliphatic aldehyde and 10 amide CO stretching was shifted up to 1690 cm-1; N-H in-plane bending at 1669 cm-1; C-H aldehyde stretching at 2861 cm-1 and H-CO bending at 1391 cm-1. [0100] Differential Scanning Calorimetry: (TA Instruments 2920 DSC), 128.460 C (endotherm), m.p.=121-124 C. (MEL-TEMP), (<strong>[298-46-4]carbamazepin</strong>e m.p.=190.20 C, p-phthalaldehyde m.p.=116 C.). [0101] Thermogravimetric Analysis: (TA Instruments 2950 Hi-Resolution TGA), 17.66% weight loss starting at 30.330 C then a 17.57% weight loss starting at 100.14 C. followed by complete decomposition. [0102] X-ray powder diffraction: (Rigaku Miniflex Diffractometer using Cu Ka (lambda=1.540562), 30 kV, 15 mA). The powder data were collected over an angular range of 30 to 40 2theta in continuous scan mode using a step size of 0.02 2theta and a scan speed of 2.0/minute. XRPD derived from the single crystal data, experimental (calculated): 8.5 (8.7); 10.6 (10.8); 11.9 (12.1); 14.4 (14.7) 15.1 (15.2); 18.0 (18.1); 18.5 (18.2); 19.8 (18.7); 23.7 (24.0); 24.2 (24.2); 26.4 (26.7); 27.6 (27.9); 27.8 (28.2); 28.7 (29.1); 29.3 (29.6); 29.4 (29.8).
3-(N'-{4-[(2-cyanoethyl)hydrazonomethyl]benzyliden}-hydrazino)propionitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In methanol;
Step 3.1: 3-(N'-{4-[(2-cyanoethyl)hydrazonomethyl]benzyliden}-hydrazino)propionitrile To a suspension of 102 g terephthaldehyde in 700 ml methanol 129.4 g of 2-cyanoethylhydrazine are added drop-wise within 20 minutes. The temperature increases to about 50 C., and an orange-red solution generally arises. After about 10 minutes further crystallization occurs. Stirring continues for 30 minutes and a precipitate that appears is filtered with suction. After washing with a little cold methanol the precipitate is dried under vacuum. 187 g of beige colored product are produced. Melting Point: 111 to 113 C. Elemental analysis: (Cl14H16N6; M=268.32)
With sodium hydroxide; In dichloromethane; water; at 0℃; for 0.25h;
100 ml of dichloromethane, 24 g of t-butoxy carbonyl methyl triphenyl phosphonium bromide and 10 g of terephalaldehyde were taken into a clean and dry round bottom flask and the resultant reaction mass was stirred for 15 minutes for attaining a homogenous solution. The reaction mass was then cooled to 0° C. followed by addition of a solution of 13.6 g of sodium hydroxide in 20.6 ml of water. The organic layer was separated and dried over 5 g of anhydrous sodium sulphate. The organic layer was then distilled completely at 40° C. The resultant residue was cooled to about 30° C. and then 50 ml of cyclohexane was added to the resultant residue followed by further cooling to about 0° C. The reaction mass was stirred at 0° C. for 1 hour followed by filtration of separated solid. The filtered solid was washed with 25 ml of cyclohexane. The filtrate was taken into a clean and dry round bottom and distilled off completely at about 65° C. to afford 11.6 grams of residue.
5-(4-(1',3-dimethyl-2,2',4,4',6'-pentaoxo-2,2',3,3',4,4',5,6'-octahydro-1H,1'H-spiro[furo[2,3-d]pyrimidine-6,5'-pyrimidin]-5-yl)phenyl)-1,1'-dimethyl-1H,1'H-spiro[furo[2,3-d]pyrimidine-6,5'-pyrimidine]-2,2',4,4',6'(3H,3'H,5H)-pentaone[ No CAS ]
With formic acid; In neat (no solvent); at 80℃; for 0.166667h;Green chemistry;
General procedure: A mixture of heteroaryl amine(2.0 mmol), terephthaldehyde (1.0 mmol) and naphthol (2.0mmol) in the presence of formic acid (0.1 mmol) as catalystwas magnetically stirred on a preheated oil bath at 80 C forthe appropriate amount of time as indicated in (Table 1). Theprogress of the reaction was monitored by thin-layer chromatography(TLC). After completion, the reaction mixture wascooled to room temperature and EtOH (5 mL) was addeduntil solid products precipitated. The precipitate was filtered,washed with cold ethanol and dried. The crude product wasstirred for 5 min in boiling EtOH and the resulting whiteprecipitate was filtered. The obtained products 7 were foundto be pure upon TLC examination (Ethyl acetate/ n-Hexane:1/2).
With formic acid; In neat (no solvent); at 80℃; for 0.25h;Green chemistry;
General procedure: A mixture of heteroaryl amine(2.0 mmol), terephthaldehyde (1.0 mmol) and naphthol (2.0mmol) in the presence of formic acid (0.1 mmol) as catalystwas magnetically stirred on a preheated oil bath at 80 ° C forthe appropriate amount of time as indicated in (Table 1). Theprogress of the reaction was monitored by thin-layer chromatography(TLC). After completion, the reaction mixture wascooled to room temperature and EtOH (5 mL) was addeduntil solid products precipitated. The precipitate was filtered,washed with cold ethanol and dried. The crude product wasstirred for 5 min in boiling EtOH and the resulting whiteprecipitate was filtered. The obtained products 7 were foundto be pure upon TLC examination (Ethyl acetate/ n-Hexane:1/2).
With piperidine; In sulfolane; at 150℃; for 1h;Reflux;
To a 3-L flask fitted with a reflux condenser charged with <strong>[939-79-7]4-cyano-2-nitrotoluene</strong> (12; 200g, 1.24mol), terephthaldehyde (83.0g, 0.62mol), and sulfolane (500mL) was added piperidine (53.0g, 0.63mol). The resulting mixture was heated at 150C for 1 h, forming an orange precipitate. The reaction was cooled to 20C, and diluted with CHCl3 (1 L). The mixture was stirred for 30min at 20C, then the precipitate was filtered and rinsed with additional CHCl3 (600mL). The resulting solids were dried to constant weight to yield 207g (79%) of product as an orange powder: mp >300C; compound is too insoluble for TLC or NMR.
With sodium hydroxide; In ethanol; at 20℃; for 0.166667h;
General procedure: Substituted ketone (5 mmol) and NaOH (0.2 g, 5 mmol) were dissolved in ethanol (20 mL) in Erlenmeyer flask and stirred at room temperature for 10 min. Aldehyde (3 mmol, 5 mL) was added and the mixture was stirred at room temperature. TLC monitoring, cold aq. 2 M HCl added in the reaction mixture to neutralize it. In most cases, the product was obtained as a pale yellow precipitate after neutralization followed by filtration under vacuum and recrystallized from ethanol.
With 1,2-dimethyl-1H-imidazol-3-ium-3-butanesulfonic acid hydrogensulfate; at 80℃; for 0.05h;Green chemistry;
General procedure: A mixture of equimolar amounts of <strong>[1074-41-5]6-amino-2-(methylthio)pyrimidin-4(3H)-one</strong> (1) (1 mmol), ethylcyanoacetateor meldrum?s acid (2 or 5) (1 mmol) and aldehyde(3 or 6) (1 mmol) was added to a vial containinga magnetic stirring bar and [DMBSI]HSO4 (0.18 mmol,0.06g) and heated at 80 C in an oil bath. Stirring at 80C was continued until disappearance of the startingmaterials. At this stage, due to the poor solubility in theionic liquid, the product appears as a precipitate. Thereaction mixture was cooled and washed with water toextract the ionic liquid. The solid obtained was recrystallizedfrom ethanol to furnish the desired pure product.The ionic liquid was recovered from the aqueous extractsby evaporation under reduced pressure, and reusedin the next run.
With acetic acid; In N,N-dimethyl-formamide; for 0.1h;Microwave irradiation;
General procedure: Acetic acid (36%) (0.5 mL) was added to a mixture of compound 3 (1.5mmol) and benzene-1,4-dicarbaldehyde (0.5 mmol) in DMF (3 ml) atroom temperature. The solution was irradiated for 5-10 min at 450 W and compound 4 was formed. After the mixture was cooled to roomtemperature, water (30 mL) was added to the reaction. The solid which formed was filtered and recrystallised from DMF-C2H5OH-H2O, to give receptors 4a-h (yield 84-99).
With sodium tris(acetoxy)borohydride; In 1,2-dichloro-ethane; at 20℃; for 1h;Inert atmosphere;
General procedure: Aldehyde (1.5 eq.) and amine (1 eq.) were mixed in 1,2-dichloroethane, followed by addition of sodium triacetoxyborohydride (1.4 eq.). The reaction was stirred at room temperature under inert atmosphere for 4 h. The reaction mixture was quenched with sat. aq. NaHCO3, and the product was extracted with ethyl acetate. The organic phasewas dried (Na2SO4),and the solvent was removed under reduced pressure. The crude product was purified by flash chromatography with ethyl acetate/acetonitrile:water:methanol (1:1:1) to afford the desired product.
In toluene; at 70℃; for 6h;Inert atmosphere; Schlenk technique;
Nitrogen substituted 100mL Schlenk tube to terephthalaldehyde 10.0g (74.4mmol), m- cresol 5g, toluene 30g was added, the reaction solution was heated up to 70 while stirring. Then, 2-amino fluorene 4.49g of (24.8 mmol) over 3 h a solution in toluene 30g was added dropwise to the solution, after stirring for subsequent 3 hours, The reaction was terminated. After the volatile solvent of the reaction solution was evaporated, the concentrated solution was vacuum-dried, and washed with hot hexane, acetonitrile, methanol. Thus 3.47 g (yield: 47%) as a pale yellow solid aromatic ring-containing compound represented by formula (III) was obtained.
With acetic acid; In ethanol; at 60℃; for 6h;Inert atmosphere;
(1) terephthalaldehyde was dissolved in 3 mL 1 mL of absolute ethanol terephthalaldehyde,Preparation of ethanol solution.(2) Weigh 0.8 mmol (0.3000 g) of <strong>[153-78-6]2-aminofluorene</strong> and 3 mL of absolute ethanol,Was added to a 50 mL three-necked flask,The three-necked flask was fixed on a magnetic stirrer,Stir evenly,And a dropping of 0.25 mL of acetic acid into a three-necked flask was used as a catalyst,The terephthalaldehyde ethanol solution prepared in step (1) was then slowly dropped into a three-necked flask through a constant pressure funnel under a nitrogen atmosphere,After refluxing in a 60 C oil bath and stirring for 6 hours,And then precipitated with anhydrous ethanol to recrystallize and dry to prepare a yellow powder. It was confirmed by infrared spectroscopy and mass spectrometry, that is, N, N '(<strong>[153-78-6]2-aminofluorene</strong>), and the mixture was cooled to room temperature. condensing terephthalaldehyde Schiff base (yield 81%,), having the formula:
75%
With acetic acid; In ethanol; at 60℃; for 6h;Inert atmosphere;
2.2mmol (0.398 g) of <strong>[153-78-6]2-aminofluorene</strong> and 12mL of absolute ethanol were added into a 50 mL three-necked flask, followed by heatin gunder nitrogen and stirring until all the reagents were completely dissolved.The solution was then dropped with 3 to 4 drops of glacial acetic acid (used as a catalyst) into the reaction. 1 mmol (0.1338 g) of p-phthalaldehyde was then dissolved in 3 mL of absolute ethanol and then slowly added into three flasks above. A pale-yellow precipitate was obtained. The whole process was protected by nitrogen to prevent oxidation of raw materials. The precipitate was then heated to 60 C,and the reaction was stopped after stirring in a water bath for 6 h at reflux.The product was then subjected to vacuum filtration after cooling to 25 C. The precipitate was dissolved in N,N-dimethylformamide (DMF) solution which was at 80 C, followed by cooling down again.The precipitate was filtered by decompress filter when it precipitated and the steps above were repeated. Impurities such as <strong>[153-78-6]2-aminofluorene</strong> and glacial acetic acid were also removed. The precipitate was washed continuously with absolute ethanol to remove higher boiling DMF solvent, and solid product was dried in vacuo. 0.32 g L2 was then obtained as a pale-yellow powder (Yield: 75%, m.p.303-305C).
33%
at 70℃; for 9h;Schlenk technique; Inert atmosphere;
In 20mL Schlenk tube purged with nitrogen 2-amino-fluorene 1.45g (7.98mmol), m- cresol 10g were charged, the reaction solution was heated to 70 C. under stirring. Thereafter, the synthesized was added dropwise to the resulting terephthalic aldehyde 0.36 g (2.66 mmol) of m- cresol 5g above solution over the solution for 3 hours, dissolved in, after then subjected to stirring for 6 hours, The reaction was terminated . After the volatile solvent of the reaction solution was evaporated, the concentrated solution was vacuum-dried, and washed with hot hexane, acetonitrile, methanol. This 0.41g (yield: 33%) as a yellow solid azomethine oligomer were obtained
In tetrahydrofuran; at 70℃; for 27h;Inert atmosphere; Schlenk technique;
Nitrogen substituted 100mL Schlenk tube to terephthalaldehyde 10.0g (74.4mmol), m- cresol 5g, the THF 30g was added, the reaction solution was heated up to 70 while stirring. Thereafter, 4,4'-methylenebis solution of (cyclohexylamine) 5.22 g (24.8 mmol) in THF30g over 3 hours was added dropwise to the above solution, after then subjected to stirring for 24 hours, The reaction was terminated. After evaporation of the volatile solvent in the reaction solution, the concentrate was vacuum dried, washed with hot hexane. Thus 7.82 g (yield: 71%) as a white solid hydrocarbon compound represented by the general formula (II) were obtained.
With potassium hydroxide; In methanol; for 3h;Reflux;
General procedure: To the stirred solutions of L/<strong>[351-50-8]D-histidin</strong>e (3.10 g, 20 mmol) and KOH(0.8 g, 20 mmol) in MeOH was added 20 ml of methanolic solution ofterephthaldehyde (1.34 g, 10 mmol). The reaction mixture was kepton a reflux for 3 h to yield a yellow colored solution (Schiff base) priorto cooling it in an ice bath. The intermediate Schiff base formed was reducedwith an excess of NaBH4 (1.13 g, 30 mmol) added in portions inMeOH containing few drops of NaOH solution at 0 C temperature andthe reaction mixture was further stirred until the yellowish color wascompletely discharged. The resulting colorless solution was filteredand acidified with acetic acid to a pH of 4.0-6.0 to yield a white solidwhich was filtered off, washed with dry MeOH and Et2O and air dried.
Weighing 1.52 g of <strong>[590-92-1]bromopropionic acid</strong>, 930 mg of 4-methylpyridine, placed in a 100 mL round bottom flask,Add 20mL of absolute ethanol, heated to reflux 24h; spin rotary liquid spinning liquid,And then continue to rinse with petroleum ether until there is a solid so far;And then weighed 670 mg of p-xylylene,Add 20 mL of absolute ethanol 20 mL, ice bath reaction 4h,A 5 mol / L NaOH solution was gradually added dropwise to the flask until the solution was slightly yellowed. After completion of the reaction,With a yellow solid to form, then add the appropriate amount of hydrochloric acid and the alkali, filter,The solid was recrystallized from methanol to a yellow powder of 1.80 g of PPV3 in 34% yield.
2,2′-(1,4-phenylene)bis(1H-indole-6-carbonitrile)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
To a solution of <strong>[939-79-7]4-cyano-2-nitrotoluene</strong> (4.0 g, 24.8 mmol) insulfolane (10 mL) was added terephthaldehyde (1.66 g, 12.4 mmol)and piperidine (1.0 g, 12.6 mmol). The resulting mixturewas heatedat 150 C for 45 min, forming an orange precipitate. The reactionwas cooled to 25 C, and diluted with CHCl3 (20 mL). The mixturewas stirred for 30 min at 25 C, then the precipitatewas filtered andrinsed with additional CHCl3 (12 mL). The resulting solids weredried to yield compound 6 (4.1 g) as an orange powder. The orangepowder was added in triethyl phosphite (50 mL). The mixture washeated to reflux for 2 days and then cooled to 25 C, anddichloromethane (50 mL) was added. The suspension was stirredfor 30 min at 25 C, then the solids were filtered and rinsed withadditional CH2Cl2 (20 mL). The resulting solids were dried to yieldcompound 7 (2.1 g, 64%) as gold-yellow powder; 1H NMR (400 Hz,DMSO-d6): d 12.21 (s, 2H), 8.07 (s, 4H), 7.86 (s, 2H), 7.73 (d,J 8.0 Hz, 2H), 7.35 (d, J 8.0 Hz, 2H), 7.19 (s, 2H).
With toluene-4-sulfonic acid; In ethanol; for 3h;Reflux;
To the dry reactor was added isophthalic acid (2.68 g, 20 mmol),50mL of ethanol and catalyst TsOH (0.15g), after stirring evenly,<strong>[15018-66-3]4-Aminoquinazoline</strong> (2.83 g, 19.5 mmol) was slowly dropped into the above ethanol solution of isophthalaldehyde. After the completion of the dropwise addition, the mixture was stirred and refluxed for 3 hours, and cooled to room temperature.2-Aminoquinazoline (2.90 g, 20 mmol) was added, and the mixture was stirred and refluxed for 3h, then cooled to room temperature. =1: 3) Separation and purification gave 5.58 g of Compound 1 in a yield of 71.9%.
With toluene-4-sulfonic acid; In ethanol;Inert atmosphere; Reflux;
Add <strong>[15018-66-3]4-aminoquinazoline</strong> (2.9 g, 20 mmol) to a dry, nitrogen-protected reactor.30mL of ethanol, terephthalaldehyde (1.34g, 10mmol),Add catalyst TsOH (0.11g), stir evenly, reflux reaction, TLC point board supervisionThe reaction was measured, the reaction was completed, cooled to room temperature, and the solvent was evaporated under reduced pressure.The obtained solid was recrystallized from ethanol/toluene and dried in vacuo to give 3.53 g of Compound 2.The yield was 91.0%.
A mixture of terephthalaldehyde (134 mg, 1.0 mmol) and triBoc-cyclam (250 mg, 500 mol) inDCM (10 mL) was stirred at ambient temperature for 2 h and then sodium triacetoxyborohydride (318mg, 1.5 mmol) was added. The mixture was stirred overnight at ambient temperature. The reaction wasquenched with aqueous NaHCO3, the layers were separated and the aqueous layer was extracted withdichloromethane. The combined organic layers were dried over anhydrous sodium sulfate andevaporated. The crude residue was purified by Combi-Flash (silica gel; ethyl acetate in hexanes) to givePKS8204 (198 mg, 64%) as a colorless gum, which turned into a fluffy solid under vacuum.
1,4-bis(5-bromo-1-methyl-1H-benzo[d]imidazol-2-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium metabisulfite; In N,N-dimethyl acetamide; at 180℃; for 0.5h;
In a microwave vial, a mixture of 4-bromo-N1 -methylbenzene-1 ,2-diamine (0.15 g, 0.74 mmol), terephthalaldehyde (0.13 g, 0.37 mmol) and sodium metabisulfite (0.19 g, 0.895 mmol) in anhydrous N,N-dimethylacetamide (5.0 ml.) was heated at 180 C for 30 min. The reaction mixture was cooled to room temperature and slowly poured into ice cold water (30 ml_). The precipitated product was collected by filtration under vacuum to obtain the crude product. The product was recrystallized from hot ethanol, filtered under vacuum and dried to obtain 1 , 4-bis(5-bromo-1 -methyl-1 H-benzo[d]imidazol-2-yl)benzene. 1 H NMR (400 MHz, DMSO-d6 ) d: 8.08 (s, 4H), 7.93 (d, J = 1 .6 Hz, 2H), 7.69 (s, 1 H), 7.67 (s, 1 H), 7.58 (d, J = 2 Hz, 1 H), 7.46 (d, J = 2 Hz, 1 H), 3.97 (s, 6H); MS (ESI + APCI): m/z = 497 [M + H]+.
1,4-bis(6-bromo-1-methyl-1H-benzo[d]imidazol-2-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium metabisulfite; In N,N-dimethyl acetamide; at 180℃; for 0.5h;
In a microwave vial, a mixture of 5-bromo-N1 -methylbenzene-1 ,2-diamine (0.20 g, 0.99 mmol), terephthalaldehyde (66 mg, 0.49 mmol) and sodium metabisulfite (0.22 g, 1 .19 mmol) in anhydrous N,N?-dimethylacetamide (5.00 ml.) was heated at 180 C for 30 min. The reaction mixture was cooled to room temperature and slowly poured into ice cold water (30 mL). The precipitated product was collected by filtration under vacuum to obtain the crude product. The product was recrystallized from hot methanol, filtered under vacuum and dried to obtain 1 , 4-bis (6-bromo-1 -methyl-1 H-benzo[d]imidazol-2-yl) benzene. 1 H NMR (400 MHz, DMSO-d6) d: 8.08 (s, 4H), 7.98 (s, 2H), 7.68 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H), 3.96 (s, 6H); MS (ESI + APCI): m/z = 497 [M + H]+.
1,4-bis(2,3-dihydrofuro[2,3-b]pyridin-2-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
With tetrabutyl ammonium fluoride; N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 60℃; for 72.0h;
To a solution of 250 mg (1.86 mmol) of terephthalaldehyde 70, 618 mg (4.47 mmol) of nitropicoline 63 in 8 mL of THF was added 4.47 mL (4.47 mmol) of a 1 M solution of TBAF and 732 mg (5.59 mmol) of Huenig's base. The mixture was stirred at 60 C for 3 days. The crude reaction mixture was concentrated under reduced pressure onto 1 g of silica gel and purified by silica gel chromatography with a gradient of 0e55% EtOH/EtOAc:hexane to afford 400 mg (68%) of dimeric furopyridine 73 as a colorless solid: mp 157e158 C; 1 H NMR (500 MHz, CDCl3) d 3.23 (dd, 2H, J 16.1 and 7.6 Hz), 3.71 (dd, 2H, J 16.1 and 9.4 Hz), 5.86 (dt, 2H, J 9.4 and 7.6 Hz), 6.85 (m, 2H), 7.45 (s, 4H), 7.50 (m, 2H), 8.01 (d, 2H, J 5.0 Hz); 13C NMR (125 MHz, CDCl3) d 36.4, 36.5, 8.10, 116.7, 119.0, 125.6, 133.4, 141.0, 146.6, 167.7. Anal. Calcd. For C20H16N2O2: C, 75.93; H, 5.10; N, 8.86. Found: C, 75.76; H, 4.98; H, 8.79.
4-(2,3-dihydrofuro[3,2-c]pyridin-2-yl)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
With tetrabutyl ammonium fluoride; N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 60℃; for 18.0h;
General procedure: To a stirred mixture of 1.00 mmol of nitropicoline 35 or 63, 1.20 mmol of the appropriate benzaldehyde, and 1.5 mmol of Huenig's base in THF (7 mL/g of nitropicoline 35/63) was added 1.3 mmol of a 1 M THF solution of TBAF. The resulting mixture was heated 60 C for 1.5e2.0 h in the case of 2,3-dihydrofuro[3,2-c] pyridines or for 18 h in the case of 2,3-dihydrofuro[2,3-b]pyridines. After cooling to room temperature, the reactions were quenched with sat. aqueous NH4Cl. The solution was extracted with EtOAc, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by silica gel chromatography as specified above.
A condenser (Condenser) A 2L round-bottom flask (2-neck round-bottomed flask) equipped with aterephthaldehyde 13.4g (0.10mol), <strong>[84405-44-7]<strong>[84405-44-7]2,7-dibromophenanthrene-9,10-dion</strong>e</strong> 69.5g (0.19mol),ammonium acetate 231 g (3.0 mol),And 1L of acetic acid was added, and then stirred at 100 C. for 24 to 48 hours to proceed with synthesis. After the reaction, the mixture was cooled to room temperature, and 800 mL of water was added thereto, followed by stirring for 30 minutes. The solid was filtered, washed several times with water, then washed with ethanol and ethyl ether, and then dried to obtain a compound represented by Chemical Formula 1-1.
With propionic acid; triethylamine; In acetonitrile;
In a 250 mL three-necked bottle,13.4 g (0.1 mol) of terephthalaldehyde was added sequentially,45.4g (0.21mol) of <strong>[1190-39-2]di-<strong>[1190-39-2]n-butyl malonate</strong></strong>,Triethylamine 0.4g,0.55g of propionic acid,70g of acetonitrile,Heated to 50 C,5 hours reaction time,Cool to 20 ,filter,Gives a white solid,After washing with a little acetonitrile,dry,51.3 g of product were obtained,Yield: 96.7%,HPLC content was 99.88%.
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