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Product Details of [ 102-04-5 ]

CAS No. :102-04-5 MDL No. :MFCD00004795
Formula : C15H14O Boiling Point : -
Linear Structure Formula :- InChI Key :YFKBXYGUSOXJGS-UHFFFAOYSA-N
M.W : 210.27 Pubchem ID :7593
Synonyms :

Calculated chemistry of [ 102-04-5 ]

Physicochemical Properties

Num. heavy atoms : 16
Num. arom. heavy atoms : 12
Fraction Csp3 : 0.13
Num. rotatable bonds : 4
Num. H-bond acceptors : 1.0
Num. H-bond donors : 0.0
Molar Refractivity : 65.71
TPSA : 17.07 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : No
CYP2D6 inhibitor : Yes
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.35 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.4
Log Po/w (XLOGP3) : 3.14
Log Po/w (WLOGP) : 3.04
Log Po/w (MLOGP) : 3.52
Log Po/w (SILICOS-IT) : 4.13
Consensus Log Po/w : 3.25

Druglikeness

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

Water Solubility

Log S (ESOL) : -3.41
Solubility : 0.0813 mg/ml ; 0.000386 mol/l
Class : Soluble
Log S (Ali) : -3.17
Solubility : 0.143 mg/ml ; 0.000679 mol/l
Class : Soluble
Log S (SILICOS-IT) : -5.68
Solubility : 0.00044 mg/ml ; 0.00000209 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.35

Safety of [ 102-04-5 ]

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

Application In Synthesis of [ 102-04-5 ]

* 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.

  • Downstream synthetic route of [ 102-04-5 ]

[ 102-04-5 ] Synthesis Path-Downstream   1~84

  • 1
  • [ 107-21-1 ]
  • [ 102-04-5 ]
  • [ 4362-53-2 ]
YieldReaction ConditionsOperation in experiment
97% With diphenylamine-terephthalaldehyde resin p-toluenesulfonate with high sulfo group content In toluene for 6h; Dean-Stark; Reflux; 4. General procedure for the synthesis of ethylene acetals catalyzed by DTRT (H) General procedure: DTRT (H) (85 mg, 1 mol%) was added to a mixture of undecanal (1a) (1.70 g, 10 mmol) and ethylene glycol (1.05 g, 17 mmol) in toluene (50 mL). The mixture was refluxed for 20 min equipped with Dean-Stark apparatus. The mixture was filtered and the precipitate was washed with toluene. The filtrate was evaporated under reduced pressure. The residue was purified by column chromatography with hexane-acetone (15 : 1) on silica gel to give acetal 1b (2.12 g, 99%).
95% With zeolite HSZ-360 In toluene for 5h; Heating;
94% With Ti(4+)-exchanged montmorillonite In toluene for 3h; Heating;
83% In benzene for 1.5h; Heating;
26% With silica gel In neat (no solvent) at 140℃; for 24h; Autoclave; Synthesis of 1,3-dioxolanes 5b-5o General procedure: Ethylene glycol (1,3.41 g, 55 mmol, 36 eq), 1.50 mmol of carbonyl compound4 (1 eq), and 50 mg (1 eq) or 500 mg (10 eq) ofsilica are placed in an autoclave (100 cm3). The sealedreactor is heated for 24 h at various temperatures. After cooling and separating the silica gel by filtration, theresidue is treated in the same manner as described above.The yields of dioxolanes are given in Tables 3 and 4.
With toluene-4-sulfonic acid; benzene Unter Entfernen des entstehenden Wassers;
With toluene-4-sulfonic acid In benzene Heating;
With sulfuric acid In toluene Heating;

  • 2
  • [ 1226-42-2 ]
  • [ 102-04-5 ]
  • [ 668-29-1 ]
YieldReaction ConditionsOperation in experiment
90% With sodium hydroxide In ethanol for 6h; Reflux; Inert atmosphere; Schlenk technique; 2.2 4.2.2. 3,4-(p-MeOPh)2-2,5-Ph2(C4CO) (5) 4,4'-Dimethoxybenzil (2.90 g, 10.36 mmol) and 1,3-diphenylacetone (2.26 g, 10.36 mmol) were dissolved in 30 mL ethanol in a 100 mL two-neck round bottom flask equipped with a condenser. The reaction mixture was warmed up nearly to the boiling point of ethanol, followed by the slow addition of a solution of 0.36 g NaOH in 3 mL ethanol. When the addition was finished, the reaction mixture was refluxed for 6 h followed by cooling to 0 °C. The crude product was then filtered and washed several times with deionized water and ethanol, and dried under vacuum overnight at room temperature to afford 5 (4.15 g, 90%) as a dark purple solid. IR (KBr) in cm-1: 1707 (s, νC=O). 1H NMR (400 MHz, CD2Cl2): δ 3.77 (s, 6H, OCH3), 6.72 (d, 4H, J = 8.0 Hz, aromatic H), 6.86 (d, 4H, J = 8.0 Hz, aromatic H), 7.20-7.29 (m, 10H, aromatic H). 13C{1H} NMR (100 MHz, CD2Cl2): δ 55.6 (OCH3), 113.7-160.3 (8 resonances, aromatic), 125.2 (C2,5 of cyclopentadienone or Cp-dienone), 154.7 (C3,4 of Cp-dienone), 200.6 (C1 of Cp-dienone). MS (ESI) m/z (relative intensity) [M+H]+: 445.
87% With sodium hydroxide In methanol for 1.25h; Reflux;
86% With potassium hydroxide In ethanol at 80℃;
81% With potassium hydroxide In ethanol for 3h; Reflux;
77% With potassium hydroxide In ethanol for 1.5h; Reflux;
75% With sodium hydroxide In ethanol at 70℃; for 0.416667h; Microwave irradiation;
66% Alkaline conditions;
64.3% With potassium hydroxide In ethanol at 75℃; for 0.5h;
With potassium hydroxide; ethanol
With potassium hydroxide In methanol
With potassium hydroxide In ethanol at 80℃; for 0.25h;

Reference: [1]He, Dongmei; Horváth, István T. [Journal of Organometallic Chemistry, 2017, vol. 847, p. 263 - 269]
[2]Location in patent: experimental part Marjani, Katayoun; Mousavi, Mohsen; Arazi, Omid; Ashouri, Akram; Bourghani, Samira; Rajabi, Mohammad [Monatshefte fur Chemie, 2009, vol. 140, # 11, p. 1331 - 1336]
[3]Thomas, K.R. Justin; Velusamy; Lin, Jiann T.; Chuen; Tao, Yu-Tai [Journal of Materials Chemistry, 2005, vol. 15, # 41, p. 4453 - 4459]
[4]Vanel, Rémi; Berthiol, Florian; Bessières, Bernard; Einhorn, Cathy; Einhorn, Jacques [Synlett, 2011, # 9, p. 1293 - 1295]
[5]Orozco, Arnoldo J.; Joachim, Kole; Ruiz, Henry D.; Fronczek, Frank R.; Isovitsch, Ralph [Luminescence, 2021, vol. 36, # 1, p. 247 - 255]
[6]Cesari, Cristiana; Sambri, Letizia; Zacchini, Stefano; Zanotti, Valerio; Mazzoni, Rita [Organometallics, 2014, vol. 33, # 11, p. 2814 - 2819]
[7]Cao, Xiaohui; Li, Si; Li, Yan; Xu, Bo; Yang, Qiusheng; Yin, Guohui; Zhang, Yuecheng; Zhao, Jiquan [Dyes and Pigments, 2022, vol. 198]
[8]He, Xinxin; Han, Xue; Wang, Huan; Wang, Bing; Wu, Bo [RSC Advances, 2016, vol. 6, # 80, p. 76514 - 76523]
[9]Dilthey et al. [Journal fur praktische Chemie (Leipzig 1954), 1934, vol. <2>141, p. 331,347][Journal fuer Praktische Chemie (Leipzig), 1935, vol. <2>142, p. 48]
[10]Justin Thomas; Velusamy, Marappan; Lin, Jiann T.; Sun, Shih-Sheng; Tao, Yu-Tai; Chuen, Chang-Hao [Chemical Communications, 2004, # 20, p. 2328 - 2329]
[11]Location in patent: experimental part Iniesta, Jesus; Matsumoto, Taisuke; Thiemann, Thies [Journal of Chemical Research, 2008, # 2, p. 109 - 114]
[12]Apps, James F. S.; Livingston, Andrew G.; Parrett, Mark R.; Pounder, Ryan J.; Taylor, Paul C.; Turner, Andrew R. [Synlett, 2014, vol. 25, # 10, p. 1391 - 1394]
  • 3
  • [ 17356-08-0 ]
  • [ 102-04-5 ]
  • [ 93020-52-1 ]
YieldReaction ConditionsOperation in experiment
44.7% With Bromotrichloromethane; potassium hydrogencarbonate In acetonitrile at 80℃; for 3h; 6 Synthesis of 4-benzyl-5-phenylthiazol-2-amine (640) A mixture of 640-1 (900 mg, 3.89 mmol), thiourea (593 mg, 7.79 mmol), CBrCl3 (1.50 mL) and KHCO3 (780 mg, 7.79 mmol) in CH3CN (10.0 mL) was stirred at 80 °C for 3 h. When the reaction was completed, it was concentrated and purified by silica gel column chromatography (petrol ether/ethyl acetate = 3/1) to afford 640 (500 mg, 44.7% yield) as a yellow solid.
With iodine
  • 5
  • [ 134-81-6 ]
  • [ 102-04-5 ]
  • [ 479-33-4 ]
YieldReaction ConditionsOperation in experiment
90% With potassium hydroxide In ethanol at 78℃;
90% With potassium hydroxide In ethanol for 2h; Reflux; 2.1 2.2.1 Synthesis of tetraphenylcyclopentadienone (1) Benzil (6.3g, 0.03mol) and 1,3-dibenzyl ketone (6.3g, 0.03mol) were dissolved in 60mL of ethanol and then heated with stirring. When the mixture started to reflux, KOH (0.8g dissolved in 8mL of ethanol) was dropped into the mixture and allowed to react for 2h until black precipitate formed. After the solution was cooled to room temperature, the precipitate was filtered and washed with ethanol for three times to obtain a black solid 17 product with yield of 90% . Melt point: 219°C. 1H NMR (CDCl3, 400MHz, ppm): δ 8.08 (d, 2H), 7.86 (m, 6H), 7.61 (dd, 2H), 7.54 (dd, 4H), 7.42 (t, 2H). 13C NMR (CDCl3, 100MHz, ppm): δ 154.2, 132.1, 131.5, 131.4, 129.0, 128.6, 128.3, 127.8, 121.7, 120.9. ESI-MS spectrometry: m/z calculated for C29H20O [M+H]+: 384.15; found: 384.16. Anal. Calcd for C29H20O: C 90.60%, H 4.16%; found: C 90.66%, H 4.17%.
85.2% Stage #1: dibenzoyl; 1,3-Diphenylpropanone In ethanol for 0.5h; Reflux; Stage #2: With potassium hydroxide In ethanol for 0.5h; Reflux;
80.6% With potassium hydroxide In ethanol for 1.75h; Reflux;
78% With sodium hydroxide In ethanol at 70℃; for 0.416667h; Microwave irradiation;
75% With potassium hydroxide In ethanol; water monomer for 0.5h; Reflux;
74% Alkaline conditions;
55% With calcium hydroxide In methanol for 5h; Reflux; 1 Preparation of compound 1-g 10 g (48 mmol) of 1,3-diphenyl-2-propanone in 250 mL-3 sphere round bottom flaskAnd benzyl 10 g (48 mmol) Was dissolved in 150 ml of methanol, and 4 g (72 mmol) of calcium hydroxide was slowly added. After refluxing for 5 hours and filtering under reduced pressure, 10.2 g of a black solid compound (yield: 55%) was obtained.
50% With potassium hydroxide In ethanol at 85℃; for 0.666667h;
30% Stage #1: dibenzoyl; 1,3-Diphenylpropanone In ethanol for 1h; Heating / reflux; Stage #2: With potassium hydroxide In ethanol for 0.5h; Heating / reflux; After benzyl (8.4 g, 40 mmol) and diphenylacetone (8.4 g, 40 mmol) were dissolved in 250 mL of ethanol and heated, the mixture was refluxed under stirring for 1 hour. KOH (2.2 g, 40 mmol) dissolved in 20 mL of ethanol was slowly added dropwise thereto, and then refluxed under stirring for 30 minutes. The resultant was slowly cooled to give a dark red solid powder. The obtained dark red solid powder was filtered under reduced pressure, and then dried under vacuum to obtain a starting material represented by Formula h (4.5 g, 30 %).[99] MS [M+H] 385
With potassium hydroxide
With ethanol; N,N,N-trimethylbenzenemethanaminium hydroxide
With potassium hydroxide; sulfuric acid 1) ethanol, reflux, 2 h, 2) acetic anhydride, reflux; Multistep reaction;
With potassium hydroxide In ethanol for 0.25h; Heating;
With potassium hydroxide In ethanol for 1h; Reflux;
With potassium hydroxide In ethanol at 80℃; for 0.25h;
With potassium hydroxide In ethanol at 78℃;

Reference: [1]Wang, Hua; Liang, Yan; Xie, Huanling; Feng, Linglong; Lu, Haifeng; Feng, Shengyu [Journal of Materials Chemistry C, 2014, vol. 2, # 28, p. 5601 - 5606]
[2]Liang, Yan [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, vol. 216, p. 395 - 403]
[3]Adamski, Michael; Skalski, Thomas J. G.; Britton, Benjamin; Peckham, Timothy J.; Metzler, Lukas; Holdcroft, Steven [Angewandte Chemie - International Edition, 2017, vol. 56, # 31, p. 9058 - 9061][Angew. Chem., 2017, vol. 129, # 31, p. 9186 - 9189]
[4]Skalski, Thomas J. G.; Britton, Benjamin; Peckham, Timothy J.; Holdcroft, Steven [Journal of the American Chemical Society, 2015, vol. 137, # 38, p. 12223 - 12226]
[5]Cesari, Cristiana; Sambri, Letizia; Zacchini, Stefano; Zanotti, Valerio; Mazzoni, Rita [Organometallics, 2014, vol. 33, # 11, p. 2814 - 2819]
[6]Pallavi, Pragyan; Bandyopadhyay, Sujoy; Louis, Jesna; Deshmukh, Arundhati; Patra, Abhijit [Chemical Communications, 2017, vol. 53, # 7, p. 1257 - 1260]
[7]Cao, Xiaohui; Li, Si; Li, Yan; Xu, Bo; Yang, Qiusheng; Yin, Guohui; Zhang, Yuecheng; Zhao, Jiquan [Dyes and Pigments, 2022, vol. 198]
[8]Current Patent Assignee: ALPHA CHEM CO LTD - KR101548694, 2015, B1 Location in patent: Paragraph 0091-0093; 0112-0114
[9]Meitinger, Nicolas; Mengele, Alexander K.; Witas, Kamil; Kupfer, Stephan; Rau, Sven; Nauroozi, Djawed [European Journal of Organic Chemistry, 2020, vol. 2020, # 42, p. 6555 - 6562]
[10]Current Patent Assignee: LG CHEM CO.,LTD. - WO2007/105884, 2007, A1 Location in patent: Page/Page column 32
[11]Dilthey; Quint [Journal fur praktische Chemie (Leipzig 1954), 1930, vol. <2> 128, p. 139,149] Johnson; Grummitt [Organic Syntheses, 1955, vol. Coll. Vol. III, p. 806]
[12]Shapiro; Becker [Journal of the American Chemical Society, 1953, vol. 75, p. 4769,4771]
[13]Samanta, S. R.; Mukherjee, A. K. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1987, vol. 26, # 1-12, p. 26 - 29]
[14]Duty, Robert C.; Farley, Thomas H. [Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 91, # 1-4, p. 271 - 280]
[15]Li, Jichao; Hu, Binbin; Hu, Gongfang; Li, Xihui; Lu, Ping; Wang, Yanguang [Organic and Biomolecular Chemistry, 2012, vol. 10, # 44, p. 8848 - 8859]
[16]Apps, James F. S.; Livingston, Andrew G.; Parrett, Mark R.; Pounder, Ryan J.; Taylor, Paul C.; Turner, Andrew R. [Synlett, 2014, vol. 25, # 10, p. 1391 - 1394]
[17]Jones, William D.; Ritz, Mikhaila D. [European Journal of Organic Chemistry, 2022, vol. 2022, # 14]
  • 6
  • [ 84-11-7 ]
  • [ 102-04-5 ]
  • [ 5660-91-3 ]
YieldReaction ConditionsOperation in experiment
92% In diethyl ether for 2h; Heating; alkali;
88.3% With sodium hydroxide In ethanol at 20℃; for 0.25h;
87% With potassium hydroxide In methanol for 0.25h; Heating;
79.3% With potassium hydroxide In ethanol for 0.5h; Inert atmosphere; Reflux;
77% With potassium hydroxide In methanol Reflux;
73% Stage #1: 9,10-phenanthrenequinone; 1,3-Diphenylpropanone In ethanol for 0.25h; Inert atmosphere; Reflux; Stage #2: With potassium hydroxide In ethanol at 0℃; for 0.25h; Inert atmosphere;
60% With potassium hydroxide In ethanol at 20 - 80℃; for 0.0833333h; 1.1-1 (Example 1) (Synthesis of Exemplified Compound No. A-7) (1-1) Synthesis of Synthesis Intermediate Compound 3Compound 1 (7 g, 32.4 mmol) , Compound 2 (7.5 g, 35.7 mmol), and 150 ml of ethanol were added to a 500-ml reaction vessel. 10 ml of ethanol in which KOH (2 g) had been dissolved were dropped to the solution at room temperature. After the complete dissolution of Compound 1 had been confirmed, the reaction vessel was placed in an oil bath at 800C, and, furthermore, 10 ml of ethanol in which KOH (2 g) had been dissolved were dropped to the resultant. After the completion of the dropping, the reaction solution was stirred for about 5 minutes, and was then, cooled with ice. After that, the precipitated crystal was filtrated and recrystallized, wherebySynthesis Intermediate Compound 3 was obtained (7.4 g, yield = 60%) .
20% With sodium hydroxide In ethanol at 70℃; for 0.416667h; Microwave irradiation;
With potassium hydroxide; ethanol
With N-benzyl-trimethylammonium hydroxide In propan-1-ol
With potassium hydroxide In methanol Heating;
With potassium hydroxide at 60℃; for 2h;
With potassium hydroxide In methanol
With potassium hydroxide In methanol
With potassium hydroxide at 80℃; for 5h; 1.2-11.2 Step 2: Add 0.75g of the phenanthrenequinone obtained in Step 1 to the alcohol solution of dibenzyl ketone and heat at 80, then add the alcohol solution of potassium hydroxide dropwise under stirring, and continue to reflux at 80 After 5h, a solution after refluxing reaction was obtained. The solution after refluxing reaction was cooled to room temperature, and a solid was precipitated after filtration. The solid was washed with methanol and dried to obtain a dark brown solid as the monocarbonyl compound 9,10-phenanthroline 1, 12-diphenylcyclopentadienone;The methanol solution of dibenzyl ketone is prepared by adding 0.75 g of dibenzyl ketone to 45 mL of methanol; the alcohol solution of potassium hydroxide is prepared by adding 400 mg of potassium hydroxide to 6 mL of methanol;

Reference: [1]Narasimhan, K.; Rajkumar, P.; Sekar, K. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1980, vol. 19, # 12, p. 1044 - 1045]
[2]Clevenger, Robert G.; Kumar, Bharat; Menuey, Elizabeth M.; Lee, Gene-Hsiang; Patterson, Dustin; Kilway, Kathleen V. [Chemistry - A European Journal, 2018, vol. 24, # 1, p. 243 - 250]
[3]Wooi, Goh Vit; White, Jonathan M. [Organic and Biomolecular Chemistry, 2005, vol. 3, # 6, p. 972 - 974]
[4]Xu, Li; Bai, Jianchun; Du, Aiqin; Yang, Zaixiao; Wu, Bo [New Journal of Chemistry, 2020, vol. 44, # 3, p. 695 - 703]
[5]Li, Yang; Zhang, Cheng; Li, Zhuang; Gu, Peiyang; Wang, Zilong; Li, Hua; Lu, Jianmei; Zhang, Qichun [Journal of Materials Chemistry C, 2019, vol. 7, # 12, p. 3512 - 3521]
[6]Karunakaran, Jayachandran; Mohanakrishnan, Arasambattu K. [Organic Letters, 2018, vol. 20, # 4, p. 966 - 970]
[7]Current Patent Assignee: CANON INC. - WO2007/123254, 2007, A1 Location in patent: Page/Page column 15-16
[8]Cesari, Cristiana; Sambri, Letizia; Zacchini, Stefano; Zanotti, Valerio; Mazzoni, Rita [Organometallics, 2014, vol. 33, # 11, p. 2814 - 2819]
[9]Dilthey; Passing [Journal fur praktische Chemie (Leipzig 1954), 1938, vol. <2> 153, p. 35,46] Dilthey; ter Horst; Schommer [Journal fur praktische Chemie (Leipzig 1954), 1935, vol. <2> 143, p. 189,200, 201]
[10]Allen,C.F.H.; Ning,R.Y. [Canadian Journal of Chemistry, 1964, vol. 42, p. 2151 - 2152]
[11]Dennis, Glen D.; Edwards-Davis, David; Field, Leslie D.; Masters, Anthony F.; Maschmeyer, Thomas; Ward, Antony J.; Buys, Irmi E.; Turner, Peter [Australian Journal of Chemistry, 2006, vol. 59, # 2, p. 135 - 146]
[12]Pauloehrl, Thomas; Welle, Alexander; Bruns, Michael; Linkert, Katharina; Börner, Hans G.; Bastmeyer, Martin; Delaittre, Guillaume; Barner-Kowollik, Christopher [Angewandte Chemie - International Edition, 2013, vol. 52, # 37, p. 9714 - 9718][Angew. Chem., 2013, vol. 125, # 37, p. 9896 - 9900,5]
[13]Current Patent Assignee: NIPPON SHOKUBAI CO LTD; OSAKA UNIVERSITY - JP2019/52117, 2019, A Location in patent: Paragraph 0057; 0058
[14]Current Patent Assignee: NIPPON SHOKUBAI CO LTD; OSAKA UNIVERSITY - JP2019/52116, 2019, A Location in patent: Paragraph 0052; 0053
[15]Current Patent Assignee: XIAN UNIVERSITY OF SCIENCE & TECHNOLOGY - CN110981680, 2020, A Location in patent: Paragraph 7-14
  • 9
  • [ 82-86-0 ]
  • [ 102-04-5 ]
  • [ 641-57-6 ]
YieldReaction ConditionsOperation in experiment
96% With potassium hydroxide In ethanol; toluene at 78℃; for 1.25h; I.b Example l.b7,9-Diphenyl-6b,7-dihydrocyclopenta[a]acenaphthylen-8-oneA suspension of 16.2 g (77 mmol) of 1 ,3-diphenylpropan-2-one and 14.2 g of acenaphthoquinone in 8.2 ml of toluene and 82 ml of ethanol was heated under reflux (78°C). Subsequently, a solution of 1.35 g of KOH and 27 ml of ethanol was added dropwise within 15 minutes. The reaction mixture was stirred under reflux for a further 1 h. The reaction mixture was cooled to 0 to 5°C. The precipitated black product was filtered off with suction and washed with 3 x 100 ml of ethanol. This gave 26.2 g (yield: 96%) of the title compound. Rf (in 10:1 toluene:ethyl acetate): 0.8.
95% With potassium hydroxide In ethanol Reflux;
94% With potassium hydroxide In ethanol; toluene for 0.0833333h; Heating;
94.6% With sodium hydroxide In ethanol at 20℃; for 0.25h;
93% With potassium hydroxide In ethanol Reflux;
92.5% With potassium hydroxide In ethanol; water at 50℃; for 3h; Inert atmosphere;
92% With sodium hydroxide In ethanol; water at 60 - 80℃; for 2h; 2.1 Example 2[0109] Synthesis of exemplified compound XX- 2[0110][Chem. 13]X9 X10 XX-2 [0111] (1) Synthesis of compound X8Reagents and a solvent described below were placed in a reactor.Compound X7 : 10 g (55 mmol)Compound X2 : 12 g (55 mmol)Ethanol: 200 ml[0112] Next, the reaction solution was heated to 60° C, and then 20 ml of a 6M aqueous sodium hydroxide solution was added dropwise to the solution. After the completion of addition, the reaction solution was heated to 80° C and stirred at this temperature (80° C) for 2 hours. Next, the reaction solution was cooled to produce precipitates which were then filtered off. Next, the resultant precipitates were washed in order with water and ethanol and then dried by heating at 80° C under reduced pressure to produce 18 g of compound X8 as a dark green solid (yield: 92%).
91% With potassium hydroxide In ethanol Heating / reflux; 1 Synthesis of ,f']-4,4'7,7'-tetraphenyl}-diindeno[1,2,3-cd:1',2',3'-lm]perylene Synthesis of ,f']-4,4'7,7'-tetraphenyl}-diindeno[1,2,3-cd:1',2',3'-lm]perylene The scheme of the overall preparation of ,f']-4,4',7,7'-tetraphenyl}-diindeno[1,2,3-cd:1',2',3'-lm]perylene is exemplified in Scheme 1. This invention is directed toward the step where XV (7,12-diphenylbenzo[k]fluoranthene) is converted to XVI and XVII. Synthesis of A: A 3 L round bottom flask was charged with 1,3-diphenylacetone (200 g, 0.95 mol), acenaphthenequinone (173.3 g, 0.95 mol) and 1.4 L of ethanol and heated to near reflux. A solution of potassium hydroxide (29.3 g, 0.52 mol) in 285 ml of ethanol was added slowly to a mechanically stirred solution under nitrogen. After complete addition the reaction (black suspension) was stirred an additional thirty minutes at reflux and then cooled to 15° C. and filtered. The solids collected were washed with another 1 L of ethanol. The solids were resuspended in 1 L of methanol and filtered. Finally, the black solids collected were washed with 1 L of methanol until the filtrate was clear to yield 307.76 g of product (91% yield). Synthesis of XV: A 3 L round bottom flask with a mechanical stirrer and reflux condenser was charged with acecyclone (100 g, 0.281 mol) and 1.2 L of 1,2-dichloroethane. The reaction vessel was affixed with two addition funnels. The first contained a solution of anthranilic acid (40.40 g, 0.295 mol) in 500 ml of 1,2-dichloroethane. The second contained isoamyl nitrite (134.8 ml, 1.003 mol) in 365 ml of 1,2-dichloroethane. After bringing the reaction mixture to reflux the solutions in the two addition funnels were added dropwise and simultaneously in equal volumes to the reaction over a period of approximately 1.4 hours. The reflux condenser must be affixed in such a manner as to return solvent directly back into the reaction mixture and not into either addition funnel solution. It is critical that the addition step be performed with great caution as the reaction is highly exothermic and effervescent. If the addition is conducted to quickly a foaming eruption will occur. It is also critical the reaction temperature be at reflux prior to initiation otherwise a buildup of diazotized anthranilic acid may occur and upon thermal initiation overwhelm the reaction vessel and thermal sink. Shortly after complete addition the bubbling ceased and the reaction color changed from black to dark yellow, indicating consumption of acecyclone. The reaction was refluxed an additional hour, and the reaction mixture solvents were stripped by simple distillation until a thick yellow paste formed. These solids were triturated with 2 L of hot butanol, collected and then triturated from hot methanol and collected, washed with 1 L of methanol and dried to provide 105.42 grams of yellow solid for a 92% yield. Thin layer chromatography, 20% dichloromethane/heptane, Rf=0.8, clean blue spot. Invention, Synthesis of XVII, Version A: A 5 L round bottom flask was fixed with a mechanical stirrer and a nitrogen inlet.
90% In ethanol; water at 60 - 80℃; Alkaline aqueous solution; 1 To 200 ml of ethanol, 9.1 g (50 mmol) E4 and 10.5 g (50 mmol) E5 were added, and the resulting mixture was heated to 60°C. To the resulting mixture, 20 ml of a 5 M aqueous sodium hydroxide solution was added dropwise. Upon completion of the dropwise addition, the mixture was heated to 80°C, stirred for 2 hours, and cooled. Precipitates were filtered, washed with water and ethanol, and vacuum-dried under heating at 80°C. As a result, 16 g (yield: 90%) of dark green solid E6 was obtained.
90.05% With potassium hydroxide In ethanol Reflux;
90% With potassium hydroxide In ethanol for 0.0833333h; Reflux; Inert atmosphere;
90% With potassium hydroxide In ethanol at 78℃; for 0.25h;
90% With potassium hydroxide In ethanol for 2h; Reflux;
90% With potassium hydroxide In ethanol for 2h; Reflux; 2.4. Synthesis of 7,9-diphenyl-8H-cyclopenta[a]acenaphthylen-8-one(DCA) DCA was synthesized through reaction of acenaphthenequinone and1,3-diphenylpropan-2-one according to literature [29]. Acenaphthenequinone(5.47 g, 0.03 mol) and 1,3-diphenylpropan-2-one (6.3 g,0.03 mol) were dissolved in ethanol (60 mL) and placed in three-neck250 mL round-bottom flask equipped with refilux condenser and magneticstirrer. When the mixture solution was heat to refilux, KOH (0.8 g)which dissolved in ethanol (5 mL) solution was dropwise added via adrop funnel. The mixture immediately turned black. After dropwiseaddition of KOH ethanol solution completed, the mixture was kept inrefilux for 2 h and then cooled down to room temperature. After filtered,black precipitate was obtained. The crude product was washed withethanol several times to obtain pure product, which is purple-black solidpowder with yield of 90%. 1H NMR (CDCl3, 300 MHz, ppm): δ 8.08 (d, J= 7.1 Hz, 2H), 7.86 (m, 6H), 7.62 (t, J = 7.5 Hz, 2H), 7.56 (t, J = 7.6 Hz,4H), 7.43 (t, J = 7.0 Hz, 2H). 13C NMR (CDCl3, 100 MHz, ppm): δ 201.7,154.2, 132.1, 131.5, 131.4, 129.0, 128.6, 128.3, 127.8, 121.7, 120.9.HRMS: m/z calcd. for C27H16O, 357.1235 [M + H]+, found: 357.1260[M + H]+. Melting point: 291 C.
89% With potassium hydroxide In ethanol for 3h; Reflux;
88% With sodium hydroxide In ethanol; water at 60 - 80℃; 1 First, 9.1 g (50 mmol) of El and 10.5 g (50 iranol) of E2 were placed in 200 ml of ethanol and heated to 6O0C, and then 20 ml of a 5M aqueous sodium hydroxide solution was added dropwise. After the addition, the resultant mixture was heated to 800C, stirred for 2 hours, and then cooled. Then, the resultant precipitates were filtered off, washed with water and ethanol, and then dried by heating at 800C under reduced pressure to prepare 15.6 g (yield: 88%) of dark green solid E3. Next, 3.56 g (10 mmol) of E3 and 2.59 g (12 mmol) of E4 were placed in 50 ml of toluene and heated to 800C, and then 1.40 g (12 mmol) of isoamyl nitrite was slowly added dropwise, followed by stirring at 1100C for 3 hours. After cooling, the mixture was washed two times with 100 ml of water each time. The resultant organic layer was washed with saturated saline and dried with magnesium sulfate. Then, the solution was filtered, and the filtrate was concentrated to obtain a brownish-red liquid. The liquid was purified by column chromatography(toluene/heptane = 2 : 3) and then recrystallized with chloroform/methanol to obtain 3.96 g (yield: 88%) of an isomer mixture as yellow crystal E5.
85% With potassium hydroxide In ethanol for 2h; Reflux; 2 Preparation of dienone 2a Preparation of dienone 2a [0270] To a solution of compound 8a (l .Og, 4.76 mmol) and acenaphthylene- 1 ,2-dione (0.87g, 1 equiv) in ethanol (20ml), under reflux was added a solution of KOH (0.28g, 1 equiv) in ethanol (5ml). After addition, the reaction mixture was stirred under reflux for additional 2hrs. On cooling, dark precipitate obtained by filtration, was washed with ethanol to afford compound 2a as a dark brown solid (yield: 85%). XH NMR (400 MHz, CDC13): δ 8.09 (d, J= 7.2 Hz, 2H), 7.89 (d, J= 8.0 Hz, 2H), 7.86 (d, J= 7.6 Hz, 4H), 7.61 (t, J= 7.6 Hz, 2H), 7.55 (t, J= 7.6 Hz, 4H), 7.43 (t, J= 7.2 Hz, 2H).
85% With potassium hydroxide In ethanol Reflux; 2 Preparation of dienone 2a To a solution of compound 8a (lOg, 4.76 mmol) and acenaphthylene-1,2-dione (O.87g, 1 equiv) in ethanol (20m1), under reflux was added a solution of KOH (O.28g, 1 equiv) in ethanol (5m1). After addition, the reaction mixture was stirred under reflux for additional 2hrs. On cooling, dark precipitate obtained by filtration, was washed with ethanolto afford compound 2a as a dark brown solid (yield: 85%). ‘H NIVIR (400 MHz, CDC13):8.09 (d, J 7.2 Hz, 2H), 7.89 (d, J 8.0 Hz, 2H), 7.86 (d, J 7.6 Hz, 4H), 7.61 (t, J 7.6 Hz, 2H), 7.55 (t, J= 7.6 Hz, 4H), 7.43 (t, J 7.2 Hz, 2H)
80% With potassium hydroxide In methanol at 90℃; for 0.5h;
77% In ethanol at 85℃; for 48h; (1) Preparation of [compound-A-1] Acenaphthenequinone (30 g, 164 mmol) and 1,3-diphenyl-2-propanone (34 g, 164 mmol) were placed in ethanol (600 mL) and then potassium hydroxide (KOH) (27.6 g, 492 mmol) was added and the mixture was stirred and refluxed at 85 ° C. for 48 hours. After lowering the temperature to ordinary temperature and adding 300 mL of water, the produced solid was filtered and dried to produce [Compound A-1] (45 g, yield 77%).
72% Stage #1: acenaphthene quinone; 1,3-Diphenylpropanone In ethanol for 0.25h; Inert atmosphere; Reflux; Stage #2: With potassium hydroxide In ethanol at 0℃; for 0.25h; Inert atmosphere;
71.3% With potassium hydroxide In ethanol Reflux; 1 Synthesis of 9-Bromo-7,12-Diphenylbenzofluoranthene Exemplary Synthesis 1; Synthesis of Compound 1; Synthesis of 9,10-Diphenylanthracene-2-Boronic Acid; An amount of 6.8 g (23.7 mmol) of 2-bromoanthraquinone was suspended in a mixed solvent of 50 ml of dehydrated toluene and 50 ml of dehydrated ether and cooled to -20° C. An amount of 26.3 ml (50 mmol) of a solution of phenyllithium (1.9 mmol/ml) in butylether was added and allowed to react for six hours. Then, distilled water was added to stop the reaction. Then, the separated organic layer was applied to column chromatography to obtain a diol form. Then, the obtained diol form, 39 g (237 mmol) of potassium iodide, and 41 g (390 mmol) of sodium hypophosphite monohydrate were dissolved in acetic acid and refluxed for six hours. After cooling, the deposit was filtered and purified by column chromatography to obtain 4.68 g (11.4 mmol) of 2-bromo-9,10-diphenylanthracene. The yield was 48.3%.An amount of 4.68 g (11.4 mmol) of 2-bromo-9,10-diphenylanthracene was dissolved in dehydrated THF and cooled to -80° C. An amount of 7.9 ml (12 mmol) of a solution of n butyllithium in n hexane was added dropwise and, 40 minutes later, 3.33 g (22.8 mmol) of triethyl borate was further added. After two-hour reaction, a dilute hydrochloric acid solution was added and the mixture was allowed to stand for 12 hours. Then, the separated organic layer was recrystallized to obtain 3.07 g (8.2 mmol) of 9,10-diphenylanthracene-2-boronic acid. The yield was 72%. Synthesis of 9-Bromo-7,12-Diphenylbenzofluoranthene; An amount of 5.9 g (32.4 mmol) of acenaphthenequinone and 7.5 g (35.7 mmol) of 1,3-diphenyl-2-propanone were suspended in 150 ml of ethanol and a solution of 2 g of potassium hydroxide in ethanol was added. After the mixture was heated to the reflux temperature, the same amount of the solution of potassium hydroxide in ethanol was further added and allowed to react for five minutes. The solid substance deposited after cooled on ice was filtered and washed with ethanol to obtain 8.24 g (23.1 mmol) of 7,9-diphenylcyclopenta[a]acenaphthylene-8-one. The yield was 71.3%.An amount of 8.24 g (23.1 mmol) of 7,9-diphenylcyclopenta[a]acenaphthylene-8-one was dissolved in 300 ml of dichloromethane and held at the reflux temperature. A solution of 5.4 g (46.2 mmol) of isoamyl nitrite in dichloromethane and a solution of 5 g (23.1 mmol) of 2-amino-5-bromobenzoic acid in dichloromethane were simultaneously added dropwise over one hour. After 12-hour reflux, methanol was added and the deposit was filtered. Then, the deposit was dissolved in xylene, refluxed for 12 hours, and purified by column chromatography to obtain 3.96 g (8.2 mmol) of 9-bromo-7,12-diphenylbenzofluoranthene. The yield was 35.5%. (Synthesis of Compound 1); An amount of 1.4 g (3.74 mmol) of 9,10-diphenylanthracene-2-boronic acid, 1.8 g (3.74 mmol) of 9-bromo-7,12-diphenylbenzofluoranthene, and 100 mg of tetrakis triphenylphosphine palladium as catalysis were dissolved in a mixed solvent of 80 ml of toluene and 20 ml of ethanol. Then, 40 ml of 2M sodium carbonate solution was added and allowed to react at 90° C. for 12 hours. After the reaction was completed, the organic layer was separated and purified by column chromatography to obtain 1.83 g (2.5 mmol) of Compound 1. The yield was 66.8%.The obtained Compound 1 was identified by the mass spectrum, infrared absorption spectrum, and NMR.
53.8% In ethanol at 75℃; for 2h; 1 1.82 g (10.0 mmol) of Compound 8, 2.62 g (12.5 mmol) of Compound 9, and 50 ml of ethanol were loaded into a 100-ml three-necked flask. In a nitrogen atmosphere, the mixture was heated to 750C, and was stirred for 2 hours . The resultant solution was cooled, and was then filtrated. The resultant black solid was washed with 10 ml..of methanol, whereby 1.91 g (53.8% yield) of Compound 10 as a blackish green solid' were obtained.
With potassium hydroxide
With potassium hydroxide; sulfuric acid 1) ethanol, reflux, 2 h, 2) acetic anhydride, reflux; Multistep reaction;
With potassium hydroxide In methanol

Reference: [1]Current Patent Assignee: BASF SE - WO2012/123888, 2012, A1 Location in patent: Page/Page column 55
[2]Location in patent: scheme or table Li, Zhanxian; Zhao, Wanying; Zhang, Yuna; Zhang, Lifeng; Yu, Mingming; Liu, Jinxia; Zhang, Hongyan [Tetrahedron, 2011, vol. 67, # 37, p. 7096 - 7100]
[3]Wehmeier, Mike; Wagner, Manfred; Muellen, Klaus [Chemistry - A European Journal, 2001, vol. 7, # 10, p. 2197 - 2205]
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[5]Kumar, Shiv; Kumar, Deepak; Patil, Yogesh; Patil, Satish [Journal of Materials Chemistry C, 2015, vol. 4, # 1, p. 193 - 200]
[6]Location in patent: experimental part Kim, Soo-Kang; Jaung, Jae-Yun; Park, Jong-Wook [Molecular Crystals and Liquid Crystals, 2009, vol. 498, p. 140 - 150]
[7]Current Patent Assignee: CANON INC. - WO2012/93578, 2012, A1 Location in patent: Page/Page column 38-39
[8]Current Patent Assignee: LG DISPLAY CO.,LTD. - US2005/222417, 2005, A1 Location in patent: Page/Page column 12
[9]Current Patent Assignee: CANON INC. - EP2243761, 2010, A1 Location in patent: Page/Page column 22
[10]Location in patent: body text Li, Zhan-Xian; Zhang, Li-Feng; Zhao, Wan-Ying; Li, Xiao-Ya; Guo, Yong-Kai; Yu, Ming-Ming; Liu, Jin-Xia [Inorganic Chemistry Communications, 2011, vol. 14, # 10, p. 1656 - 1658]
[11]Location in patent: experimental part Li, Zhanxian; Zhang, Lifeng; Li, Xiaoya; Guo, Yongkai; Ni, Zhonghai; Chen, Jianhong; Wei, Liuhe; Yu, Mingming [Dyes and Pigments, 2012, vol. 94, # 1, p. 60 - 65]
[12]Wang, Hua; Liang, Yan; Wang, Yike; Xie, Huanling; Feng, Linglong; Lu, Haifeng; Feng, Shengyu [RSC Advances, 2014, vol. 4, # 33, p. 17171 - 17178]
[13]Xie, Huanling; Wang, Hua; Xu, Zhen; Qiao, Ruijing; Wang, Xuefeng; Wang, Xianming; Wu, Lianfeng; Lu, Haifeng; Feng, Shengyu [Journal of Materials Chemistry C, 2014, vol. 2, # 44, p. 9425 - 9430]
[14]Feng, Shengyu; Lu, Haifeng; Wang, Hua; Xu, Lichao [Dyes and Pigments, 2021, vol. 193]
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[16]Current Patent Assignee: CANON INC. - WO2011/1741, 2011, A1 Location in patent: Page/Page column 47-48
[17]Current Patent Assignee: UNIVERSITY SYSTEM OF GEORGIA - WO2015/191616, 2015, A1 Location in patent: Paragraph 0270
[18]Current Patent Assignee: UNIVERSITY SYSTEM OF GEORGIA - WO2018/93924, 2018, A1 Location in patent: Paragraph 0294
[19]Andrew, Trisha L.; Cox, Jason R.; Swager, Timothy M. [Organic Letters, 2010, vol. 12, # 22, p. 5302 - 5305]
[20]Current Patent Assignee: LG CHEM CO.,LTD. - JP2016/505507, 2016, A Location in patent: Paragraph 0143; 0144
[21]Karunakaran, Jayachandran; Mohanakrishnan, Arasambattu K. [Organic Letters, 2018, vol. 20, # 4, p. 966 - 970]
[22]Current Patent Assignee: FUTABA CORPORATION - US2011/295017, 2011, A1 Location in patent: Page/Page column 21-22
[23]Current Patent Assignee: CANON INC. - WO2007/114038, 2007, A1 Location in patent: Page/Page column 68
[24]Dilthey; ter Horst; Schommer [Journal fur praktische Chemie (Leipzig 1954), 1935, vol. <2> 143, p. 189,200, 201]
[25]Tsuge, Otohiko; Okita, Shigeru; Noguchi, Michihiko; Watanabe, Haruyuki [Chemistry Letters, 1981, p. 1439 - 1442]
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  • 10
  • [ 50-00-0 ]
  • [ 6091-44-7 ]
  • [ 102-04-5 ]
  • [ 70552-69-1 ]
  • 12
  • [ 35578-47-3 ]
  • [ 102-04-5 ]
  • [ 38268-11-0 ]
YieldReaction ConditionsOperation in experiment
93% With potassium hydroxide; In ethanol; for 1h;Inert atmosphere; Reflux; 4,4?-Dibromobenzyl (20 g, 54.3 mmol), 1,3-diphenylpropan-2-one (11.43 g, 54.4 mmol), and potassium hydroxide (3.35 g, 54.4 mmol) were placed in a flask having been substituted with nitrogen, dissolved in 100 mL of ethanol and refluxed for 1 hour. Thereafter, the reaction solution was cooled to 0 C., impurities were removed with Celite, and the product was rinsed with ethanol to provide an intermediate (7) as a violet solid matter (26 g, 93%). 1H NMR (500 MHz, CDCl3): 7.34 (dd, J=8.5 Hz, 2.0 Hz, 4H), 7.26 (d, J=8.0 Hz, 6H), 7.20-7.18 (m, 4H), 6.80 (dd, J=8.5 Hz, 2 Hz, 4H)
62% After 4,4'-dibromobenzyl (9.8 g, 27 mmol) and diphenylacetone (6.2 g, 30 mmol) were dissolved in 250 mL of ethanol and heated, the mixture was refluxed under stirring for 1 hour. KOH (1.64 g, 30 mmol) dissolved in 20 mL of ethanol was slowly added drop wise thereto, and then refluxed under stirring for 30 minutes. The resultant was slowly cooled to give a dark red solid powder. The obtained dark red solid powder was filtered under reduced pressure, and then dried under vacuum to obtain a starting material represented by Formula j.[109] (9.0 g, 62 %); 1H NMR (400 MHz, DMSO-J ) 7.50-7.47 (d, 4H), 7.33-7.27 (m, 6H),7.17-7.15(d, 4H), 6.94-6.92(d, 4H) ; MS [M+H] 540,542,544
  • 13
  • [ 102-04-5 ]
  • [ 1788-31-4 ]
YieldReaction ConditionsOperation in experiment
100% With acetic acid; acetone oxime at 135℃; for 1.5h;
98% With hydroxylamine hydrochloride; glycine In N,N-dimethyl-formamide at 25℃; for 6h;
96% With hydroxylamine hydrochloride; sodium acetate In ethanol; water Reflux;
96% With hydroxylamine hydrochloride; sodium hydroxide In ethanol; water at 0 - 20℃; for 24h; General Procedure for Synthesis of ketoximes (1a-1zd) General procedure: To a 50 mL round bottom flask, ketone (10.0 mmol) and hydroxylamine hydrochloride (15.0mmol) were added in 25 mL ethanol/ water (4:1). A quantity of NaOH solution was added top H=9 in ice bath, stirred at room temperature for 24 hours. The mixture was then extracted with ethyl acetate (3 × 20 mL). The combined organic extracts were dried over Mg2SO4 and concentrated under reduced pressure. The ketoxime products were obtained by recrystallization of ethyl acetate or petroleum ether.
93% With hydroxylamine hydrochloride; sodium acetate In ethanol; water Reflux; General Procedure A1: Synthesis and Characterization of Oximes General procedure: To a 100 mL round bottom flask charged with a stir bar, sodium acetate (1.64 g, 20.0mmol,) and hydroxylamine hydrochloride (1.04 g, 15.0 mmol), was added a solution ofthe ketone (0.3 M) in ethanol/water (4:1). The reaction mixture was then heated toreflux until all the ketone starting material was consumed as indicated by TLC. After reflux, the reaction was allowed to cool to room temperature. The crude mixture wasobtained after removal of excess ethanol. To the crude mixture was added 20 mL ofwater. The resulting aqueous solution was extracted with ethyl acetate (20 mL × 3).The combined organic layers were then washed with water (20 mL × 2) and brine (20mL × 1), dried over anhydrous MgSO4, filtered and concentrated. The oxime productwas used directly in the next step. In certain cases, the oxime product was obtained afterflash column chromatography or recrystallization using the indicated solvent mixture.
90% With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 80℃; Inert atmosphere;
70% With hydroxylamine hydrochloride; sodium hydroxide In methanol Milling; SI-2. Synthesis of 1,3-diphenylpropan-2-one oxime (S1). [[i]] A sample of the 1,3-diphenylpropan-2-one (10.0 mmol) and hydroxylamine hydrochloride ([NH2OHHCl]/[ketone]= 1.20 molar ratio) were mixed in a mortar in air. Finely grinded NaOH was added ([NH2OHHCl]/[NaOH] = 1.0 molar ratio), together with methanol (2.0 ml) and the mixture was finely grinded for ten minutes. Methanol was added in small portions during this time interval (5.0 ml), then the slurry was evaporated in air. The solid residue was treated with portions of chloroform to extract the reaction product. The solvent was eliminated under vacuum and solid product (1,3-diphenylpropan-2-one oxime (S1)) was obtained (70% isolated yield). The compound showed: IR (ATR, cm-1): 3300, 1650, 1603, 1496, 1405, 970; 1H-NMR: 8.81 (1H, OH); 3.70 (s, 2H, CH2Ph); 3.49 (s, 2H, CH'2Ph); 7.30 (m, 10H, Harom); 13C-NMR: 159.1, 136.6, 136.4, 129.3, 129.2, 128.6 (2C), 126.8, 126.5, 39.7, 32.6.
With ethanol; hydroxylamine hydrochloride; sodium acetate
With hydrogenchloride; ethanol; hydroxylamine hydrochloride
With sodium hydroxide; hydroxylamine hydrochloride In ethanol; water for 1h; Heating;
With pyridine; hydroxylamine In ethanol at 60℃;
With hydroxylamine hydrochloride; water; sodium hydroxide In ethanol at 20℃; for 24h;
With pyridine; hydroxylamine hydrochloride In ethanol for 18h; Reflux;
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃;
With ammonium hydroxide hydrochloride; sodium acetate In methanol; water at 20℃;
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; Inert atmosphere; Synthesis and spectra data of 2H-azirines General procedure: General Procedure: A solution of ketone (1 equiv), NH2OH•HCl (1.5 equiv) and sodium acetate in a mixture solvent of MeOH/H2O (20:1) was stirred at rt. When the reaction completed (indicated by TLC), the organic solvent was removed in vacuo and extracted by DCM. The combined organic phase was washed with sat. NaHCO3 (aq.), brine sequentially, and then dried over anhydrous Na2SO4. After removing the solvent, the crude oxime was used directly for the next step.
With hydroxylamine hydrochloride; sodium acetate In methanol at 20℃; Inert atmosphere;

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[2]Maheswara, Muchchintala; Siddaiah, Vidavalur; Gopalaiah, Kovuru; Rao, Vallabhaneni Madhava; Rao, Chunduri Venkata [Journal of Chemical Research, 2006, # 6, p. 362 - 363]
[3]Mo, Xiaobin; Morgan, Timothy D. R.; Ang, Hwee Ting; Hall, Dennis G. [Journal of the American Chemical Society, 2018, vol. 140, # 15, p. 5264 - 5271]
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[6]Gao, Yu; Liu, Jingjing; Li, Zhenjiang; Guo, Tianfo; Xu, Songquan; Zhu, Hui; Wei, Fulan; Chen, Siming; Gebru, Hailemariam; Guo, Kai [Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 2040 - 2049]
[7]Belli Dell' Amico, Daniela; Colalillo, Marialuigia; Labella, Luca; Marchetti, Fabio; Samaritani, Simona [Inorganica Chimica Acta, 2018, vol. 470, p. 181 - 186]
[8]Neber; Uber [Justus Liebigs Annalen der Chemie, 1928, vol. 467, p. 54,62]
[9]Rattner [Chemische Berichte, 1888, vol. 21, p. 1316,1317]
[10]Harada; Ohno; Kobayashi; Mukaiyama [Synthesis, 1991, # 12, p. 1216 - 1220]
[11]Gopalsamy, Ariamala; Yang, Hui; Ellingboe, John W.; McKew, John C.; Tam, Steve; Joseph-McCarthy, Diane; Zhang, Wen; Shen, Marina; Clark, James D. [Bioorganic and Medicinal Chemistry Letters, 2006, vol. 16, # 11, p. 2978 - 2981]
[12]Location in patent: experimental part Soltani Rad, Mohammad Navid; Khalafi-Nezhad, Ali; Karimitabar, Fatemeh; Behrouz, Somayeh [Synthesis, 2010, # 10, p. 1724 - 1730]
[13]Gerfaud, Thibaud; Wei, Hai-Long; Neuville, Luc; Zhu, Jieping [Organic Letters, 2011, vol. 13, # 23, p. 6172 - 6175]
[14]Xuan, Jun; Xia, Xu-Dong; Zeng, Ting-Ting; Feng, Zhu-Jia; Chen, Jia-Rong; Lu, Liang-Qiu; Xiao, Wen-Jing [Angewandte Chemie - International Edition, 2014, vol. 53, # 22, p. 5653 - 5656][Angew. Chem., 2014, vol. 126, # 22, p. 5759 - 5762,4] Hu, Haipeng; Liu, Yangbin; Lin, Lili; Zhang, Yuheng; Liu, Xiaohua; Feng, Xiaoming [Angewandte Chemie - International Edition, 2016, vol. 55, # 34, p. 10098 - 10101][Angew. Chem., 2016, vol. 128, p. 10252 - 10255,4]
[15]Zhu, Lei; Yu, Yinghua; Mao, Zhifeng; Huang, Xueliang [Organic Letters, 2015, vol. 17, # 1, p. 30 - 33]
[16]Xu, Ze-Feng; An, Yuehui; Chen, Yidian; Duan, Shengguo [Tetrahedron Letters, 2019, vol. 60, # 28, p. 1849 - 1853]
[17]Lavernhe, Rémi; Torres-Ochoa, Rubén O.; Wang, Qian; Zhu, Jieping [Angewandte Chemie - International Edition, 2021, vol. 60, # 45, p. 24028 - 24033][Angew. Chem., 2021, vol. 133, # 45, p. 24230 - 24235]
  • 14
  • [ 102-04-5 ]
  • [ 1081-75-0 ]
YieldReaction ConditionsOperation in experiment
88% With polymethylhydrosiloxane; tris(pentafluorophenyl)borate In dichloromethane at 20℃;
80% With potassium hydroxide; hydrazine hydrate In water for 2h; Heating;
With hydrogenchloride; amalgamated zinc
With potassium hydroxide; hydrazine hydrate; diethylene glycol oder in Triaethylenglykol;
With hydrogen; nickel at 400℃;
With phosphorus; hydrogen iodide at 180℃;
Stage #1: 1,3-Diphenylpropanone With 1,3-propanedithiol copolymer; boron trifluoride diethyl etherate In chloroform at 0℃; for 10h; Stage #2: With ammonia; sodium In tetrahydrofuran for 0.5h;
Multi-step reaction with 3 steps 1: sodium tetrahydroborate / ethanol / 1 h / 20 °C 2: carbon tetrabromide; triphenylphosphine / dichloromethane / 24 h / 0 - 20 °C / Inert atmosphere 3: water; zinc / acetonitrile / 4 h / 80 °C / Sealed tube; Inert atmosphere
Multi-step reaction with 2 steps 1.1: sodium tetrahydroborate / ethanol / 1 h / 20 - 30 °C 1.2: 24 h / 0 - 30 °C / Inert atmosphere 2.1: water; zinc / acetonitrile / 4 h / 80 °C / Inert atmosphere; Sealed tube
86 %Chromat. With manganese; (1,2-dimethoxyethane)dichloronickel(II); 1,1,3,3-Tetramethyldisiloxane; potassium <i>tert</i>-butylate; 1,3-bis(cyclohexyl)imidazolium tetrafluoroborate In toluene at 70℃; for 5h;

  • 15
  • [ 102-04-5 ]
  • [ 958-79-2 ]
YieldReaction ConditionsOperation in experiment
88% With bromine In acetic acid at 20℃; for 0.5h; Inert atmosphere;
79% With bromine; acetic acid at 23℃; for 0.5h; Inert atmosphere;
79% With bromine In acetic acid at 23℃; for 0.5h; Inert atmosphere;
With carbon disulfide; bromine
With bromine; acetic acid
With aluminium trichloride; bromine In diethyl ether
With bromine; acetic acid for 3h;
With bromine; acetic acid for 3h;
With bromine; acetic acid for 3h;
With bromine In acetic acid for 3h;

  • 16
  • [ 102-04-5 ]
  • [ 4275-43-8 ]
YieldReaction ConditionsOperation in experiment
81% With nickel(II) tetrafluoroborate hexahydrate; ammonia; hydrogen; bis(2-diphenylphosphinoethyl)phenylphosphine In 2,2,2-trifluoroethanol at 120℃; for 24h; chemoselective reaction;
67.7% With ammonium acetate; sodium cyanoborohydride In methanol at 0 - 25℃; for 3h; 8.1 Step 1: 1,3-Diphenylpropan-2-amine (2): To a solution of dibenzyl ketone (500 mg, 2.38 mmol) in MeOH (10 mL) was added ammonium acetate (1.83 g, 23.78 mmol) and NaBH3CN (300 mg, 4.76 mmol) at 0 °C and the mixture was stirred at 25 °C for 3 hours. The reaction mixture was quenched with iN aqueous NaOH solution and extracted with EtOAc twice. The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated todryness. The residue was purified by column chromatography via silica gel (eluted with DCM:MeOH= 200: 1 to 20: 1) to afford compound 2 (340 mg, yield 67.7%) as colorless oil. LC/MS (ESI) m/z: 212(M+H)t
With ammonium formate at 220℃; anschliessend Behandeln mit aethanol.Kalilauge;
With methanol; ammonia; nickel Hydrogenation;
Multi-step reaction with 2 steps 1: 175 °C 2: aq.-ethanolic sulfuric acid
With ammonium acetate; sodium cyanoborohydride In methanol at 20℃; for 40h;
Stage #1: 1,3-Diphenylpropanone With ammonium acetate In methanol at 20℃; for 1.5h; Inert atmosphere; Stage #2: With methanol; sodium cyanoborohydride at 20℃; for 56h; Inert atmosphere;

  • 17
  • [ 485-47-2 ]
  • [ 102-04-5 ]
  • [ 6583-74-0 ]
YieldReaction ConditionsOperation in experiment
84% With potassium hydroxide In methanol; ethanol at 75℃; for 1h;
81.9% With potassium hydroxide In methanol; ethanol at 75℃; for 3h;
75% Stage #1: indan-1,2,3-trione hydrate; 1,3-Diphenylpropanone In ethanol at 20℃; for 0.5h; Inert atmosphere; Stage #2: With tetra(n-butyl)ammonium hydroxide In ethanol; water for 1h; Inert atmosphere; Reflux;
72% With potassium hydroxide In methanol; ethanol at 80℃; for 1h; Inert atmosphere; 1 1,3-phenylcyclopenta[a]indene-2,8-dione (1) 1,3-diphenylpropan-2-one (4.62 g, 0.022 mol) was added to asuspension of ninhydrin (4.02 g, 0.023 mol) in absolute ethanol(50 ml). Subsequently, the MeOH/KOH solution (5 ml) was instilledin portions (5e6 drops) every 15 min of reaction. The stirred reactionmixture turned red after adding first portion, and finallyafter last portion it turned violet. The reaction ended after 1 hheating in 80 C. Obtained violet crystals (5.87 g) was washed withcold methanol (120 ml) and then recrystallized from acetonitrile(yield 72%). The structure of final product is already known [9],therefore full spectrochemical analysis was not performed. Mp.205e206 C. C24H14O2, M 334.37 gmol-1. 1H NMR (CDCl3)d (ppm): 7.42e7.56 (m, 6H, CHarom); 7.70e7.77 (m, 4H, CHarom);8.04e8.10 (m, 1H, CHarom); 8.18e8.24 (m, 1H, CHarom); 8.59e8.64(m, 2H, CHarom). ESI MS: m/z 357.1 [M Na] (100%).
In ethanol
With triethylamine In ethanol
With potassium hydroxide In methanol; diethyl ether

  • 19
  • [ 103-82-2 ]
  • [ 5830-30-8 ]
  • [ 6683-94-9 ]
  • [ 102-04-5 ]
  • 20
  • [ 7033-39-8 ]
  • [ 102-04-5 ]
  • 2,4-dimethyl-7,9-diphenyl-2,4-diazabicyclo[4,3,0]nonane-3,5,8-trione [ No CAS ]
  • 21
  • [ 26275-88-7 ]
  • [ 102-04-5 ]
  • [ 103-82-2 ]
  • [ 3225-26-1 ]
  • [ 100-52-7 ]
  • [ 100-51-6 ]
  • 22
  • [ 1788-31-4 ]
  • [ 102-04-5 ]
YieldReaction ConditionsOperation in experiment
90% With copper(II) sulfate In tetrahydrofuran; methanol; water for 19h; Heating;
81% With iron pentacarbonyl In methanol for 48h; Irradiation; Fe2(CO)9, 60 deg C;
32% With water; oxygen In acetonitrile at 60℃; for 6h; Autoclave; Green chemistry; General experimental procedure for deoximation to the corresponding carbonyl compounds General procedure: Oximes (1.0 mmol), Amberlyst-15 (0.02 g), FPA53-NO2(0.02 g), and solvent (1.5 mL) were introduced into a 25-cm-high, 90-mL autoclave with a glass tube inside equipped with magnetic stirrer (Scheme 2). Then the autoclave was charged with oxygen to 0.1 MPa. The reaction mixture was stirred at desirable temperature for special time. Progress of the reaction was monitored by thin-layer chromatography (TLC) or gas chromatography (GC). After the reaction, the resin (Amberlyst-15 and FPA53-NO2) was separated from the reaction mixture by filtration and extracted with 3 mL CH3CN (2 1.5 ml). The solvent was removed under reduced pressure. The residue was further purified by column chromatography on silica gel (300 mesh) with hexane/ethyl acetate to give the corresponding carbonyl compounds.
With bismuth(lll) trifluoromethanesulfonate; bismuth(III) bromide In water; acetone; acetonitrile for 4h; Heating;
Multi-step reaction with 2 steps 1: acetic acid; chlorine 2: NaN3; aqueous acetic acid; CO2

  • 24
  • [ 122-78-1 ]
  • [ 60-12-8 ]
  • [ 1081-75-0 ]
  • [ 108-88-3 ]
  • [ 102-04-5 ]
YieldReaction ConditionsOperation in experiment
1: 60 % Chromat. 2: 3 % Chromat. 3: 8 % Chromat. With carbon monoxide; hydrogen In pyridine at 140℃; for 12h; Further byproducts given. Title compound not separated from byproducts;
  • 25
  • [ 5334-31-6 ]
  • [ 102-04-5 ]
  • 3-carboxamido-4,7-dihydro-5,7,7-tribenzyl-6-phenylpyrazolo<1,5-a>pyrimidine [ No CAS ]
  • 26
  • [ 100-63-0 ]
  • [ 102-04-5 ]
  • [ 4679-91-8 ]
YieldReaction ConditionsOperation in experiment
100% With trichloroacetic acid at 100℃; for 0.0833333h;
80% With phosphorus trichloride In benzene
80% With Amberlite IR 120 In ethanol at 80℃; for 12h; EXPERIMENTAL General procedure: A mixture of the carbonyl compound (5, 1.0 mmol), arylhydrazine (6, 1.2 mmol), and the solid acid (7, Amberlite, 1.5 g, obtained from Aldrich Chemical Co.) was refluxed in absolute ethanol (10 ml) for 8 h. The reaction was monitored by thin-layer chromatography(TLC), and upon completion the mixture was cooled to room temperature, the catalyst filtered off, and the product was washed thoroughly with ethylacetate (30 ml). The combined organics were washed with water, dried (Na2SO4), and concentrated in vacuo. The resulting residue was chromatographed on a silicagel column eluting with ethylacetate-hexane mixtures to obtain the purified indole (8). This was fully characterized by infrared, 400-MHz 1H NMR, high-resolution mass spectrometry, and melting point (solids).
77% With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide In ethyl acetate at 110℃; for 0.25h; Microwave irradiation; Sealed vessel; 1. Typical procedure for a T3P mediated Fischer indole synthesis General procedure: T3P (50% in EtOAc) (0.55-0.68 mmol) was added to a mixture of hydrazine (59 mg, 0.55 mmol) and ketone/aldehyde (0.55 mmol) in a microwave vial. The reaction volume was then made up to 0.5 mL with EtOAc and the vessel was sealed under air. The mixture was heated under microwave irradiation (Biotage Initiator) at 100-150 °C for 5-15 min. The solvent was evaporated under reduced pressure and the oily residue was purified by filtration through a plug of silica gel (eluent: isohexane/EtOAc, 8:2) to yield the desired indole or tetrahydrocarbazole. When the reaction was conducted on a 5 mmol scale the product (3a) was purified by precipitation from acetone/water.

  • 28
  • [ 6217-22-7 ]
  • [ 102-04-5 ]
  • [ 108868-49-1 ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide; In methanol; at 20℃;Inert atmosphere; Reflux; 32.63 g (139.8 mmol) of compound (II) and 31.08 g (147.4 mmol) of 1,3-diphenylacetone (III) are dissolved in 4500 ml of methanol. The orange suspension is heated under reflux, and a potassium hydroxide solution (7.76 g) in methanol (31 ml) is slowly added dropwise. An immediate black-violet coloration occurs. The mixture is heated under reflux for 60 min and subsequently stirred overnight at room temperature. After filtration, the precipitate is washed with cold methanol, dried under reduced pressure and reacted without further purification. The yield is 41.89 g (103.1 mmol), corresponding to 73% of theory
  • 29
  • [ 34461-00-2 ]
  • [ 102-04-5 ]
  • [ 2423-73-6 ]
YieldReaction ConditionsOperation in experiment
93% With sodium hydroxide In ethanol; water for 48h; Ambient temperature;
  • 30
  • [ 693-03-8 ]
  • [ 102-04-5 ]
  • [ 84735-51-3 ]
YieldReaction ConditionsOperation in experiment
98% With cerium(III) chloride In tetrahydrofuran at 0℃; for 0.5h;
93% With cerium(III) chloride In tetrahydrofuran at 0℃; for 1h;
82% With cerium(III) chloride In tetrahydrofuran 1.) 0 deg C, 2 h, 2.) 0 deg C, 0.5 h;
20% In tetrahydrofuran 1.) -78 deg C, 3 h 2.) 0 deg C, 1 h;

  • 31
  • [ 50-00-0 ]
  • [ 102-04-5 ]
  • [ 19066-35-4 ]
YieldReaction ConditionsOperation in experiment
With ammonium acetate
With ammonium acetate
With ammonium acetate In ethanol for 6h; Reflux; 2 Synthesis of the novel molecule was performed in a glass or stainless steel reactor having a convex bottom and provided with reflux condenser, heating jacket and adjustable-speed stirrer.210 g dibenzylketone, 120 g formaldehyde and 230 g ammonium acetate were introduced in the reactor along with 500 ml 96° ethanol.The mixture was heated to the boil.Synthesis reaction was under reflux for a maximum time of 6 h and conducted under a hood. Prior to stopping the reaction, a sample of precipitate was collected and, after having washed it with ethanol, correspondence with an IR spectrum was checked.When results were consistent, heating was stopped and precipitate cooled and collected; the latter was purified by washing (with ethanol) or solubilization and recrystallization.
  • 32
  • [ 75-77-4 ]
  • [ 102-04-5 ]
  • [ 79990-96-8 ]
YieldReaction ConditionsOperation in experiment
55% Stage #1: 1,3-Diphenylpropanone With sodium hydride In tetrahydrofuran; hexane for 3h; Inert atmosphere; Reflux; Stage #2: chloro-trimethyl-silane With triethylamine In tetrahydrofuran; hexane Synthesis of 1-iodo-1,3-diphenylpropan-2-one 5 1,3-Diphenyl-propan-2-one 1a (1.05 g, 5 mmol) in dry THF (10 ml) was added to a stirred suspension of hexane-washed sodium hydride (0.40 g of a 60 % dispersion in oil, 10 mmol) in dry THF (10 ml) under argon and refluxed for 3 hr, before cooling to room temperature. Dry triethylamine (1.05 ml, 7.2 mmol) and chlorotrimethylsilane (1.24 ml, 7.2 mmol) were added, forming a white precipitate, the mixture stirred for 15 min, diluted with ether (50 ml), washed with cold saturated sodium bicarbonate solution (3x20 ml), brine (20 ml), dried with MgSO4 and evaporated under reduced pressure to give the crude silyl enol ether (b) in 55% yield as a pale yellow oil. To a stirred the KI (2.2 equiv) in methanol (10 ml), 96% lead() acetate (3.3 equiv) and the enolate b (5 mmol) in methanol (5 ml) are added successively at 10 °C, and stirring is continued for 10 min. The reaction mixture is poured into a solution of ice-cold water (50 ml) and 10% hydrochloric acid (20 ml), and extracted with ether (3×50 ml). The combined ether extract is washed successively with saturated sodium hydrogen carbonate solution (20 ml), sodium thiosulfate solution (10 ml), brine (20 ml), and dried with sodium sulfate, purified by column chromatography on silica gel. Product 5 was obtained in 27% yield as a yellow solid.
With magnesium bis(hexamethyldisilazide) 1.) DME, HMPA, -75 deg C, 3 h, 2.) -75 deg C, 30 min; Yield given. Multistep reaction;
With triethylamine; sodium iodide In acetonitrile at 20 - 25℃; for 12h; Inert atmosphere;
  • 33
  • [ 1885-38-7 ]
  • [ 102-04-5 ]
  • [ 78267-09-1 ]
  • 34
  • [ 3225-26-1 ]
  • [ 102-04-5 ]
  • 4-benzoyloxy-1-benzyloxy-2,2,6,6-tetramethylpiperidine [ No CAS ]
  • 4-benzoyloxy-2,2,6,6-tetramethyl-1-phenylacetoxy-piperidine [ No CAS ]
  • 35
  • [ 2921-14-4 ]
  • [ 102-04-5 ]
  • (1-Benzyl-2-phenyl-ethylideneaminooxy)-acetic acid [ No CAS ]
  • 36
  • [ 151-50-8 ]
  • [ 102-04-5 ]
  • [ 23186-94-9 ]
YieldReaction ConditionsOperation in experiment
70% With ammonium carbonate In ethanol at 60℃; for 15h;
  • 37
  • [ 102-04-5 ]
  • [ 66223-95-8 ]
YieldReaction ConditionsOperation in experiment
98% With water-d2; potassium hydroxide at 20℃; for 72h; Inert atmosphere;
75% With deuteriated sodium hydroxide In water-d2 for 15h; Heating;
With water-d2; sodium carbonate for 19h; Heating;
With water-d2; potassium carbonate In 1,4-dioxane at 85 - 90℃; for 48h;

  • 38
  • [ 6914-71-2 ]
  • [ 102-04-5 ]
  • 5,5-dibenzyl-2-methoxycarbonyl-5-pentanolide [ No CAS ]
  • 39
  • [ 3363-97-1 ]
  • [ 102-04-5 ]
  • [ 3432-73-3 ]
YieldReaction ConditionsOperation in experiment
88% With potassium hydroxide In ethanol for 1.75h; Reflux;
80% With potassium hydroxide In methanol; ethanol; toluene at 130℃; for 1h; 4 Preparation of 1,4'-bis(2,4,5-triphenylcyclopentadienone)benzene (BTPCPB) To a flask, p-di(phenylglyoxalyl)benzene (10 g, 0.03 mol) and 1,3'-diphenylacetone was dissolved in 100 mL of ethanol with 10 mL of toluene. And solution of potassium hydroxide (2.1 g, 0.04 mol) in 10 mL of methanol was added dropwise to this solution at room temperature. After dropping, the mixture was refluxed for 1 h at 130 °C. The resulting mixture was cooling to 0 °C and crystalized itself. The solid collected by filtration and washed with cold ethanol. Filtered product was dried in vacuum at 60 °C for 24 h (yield = 80%).
69.7% Stage #1: 1,4-bis(phenylglyoxalyl)benzene; 1,3-Diphenylpropanone In ethanol for 1h; Reflux; Stage #2: With potassium hydroxide In ethanol for 1h; Reflux;
With N-benzyl-trimethylammonium hydroxide In methanol
With potassium hydroxide for 0.75h; Reflux;

  • 41
  • [ 26254-35-3 ]
  • [ 102-04-5 ]
  • 3-bromo-7,9-diphenyl-8H-cyclopenta[a]acenaphthylen-8-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% With potassium hydroxide In ethanol; water at 60 - 80℃; 1 [00101] Into 200 mL of ethanol, 13.1 g (50 iranol) of E4 and 10.5 g (50 mmol) of E5 were charged, and the solution was heated to 600C. Subsequently, 20 mL of a 5M aqueous potassium hydroxide solution was added dropwise to the solution. After the dropwise addition, the reaction mixture was heated to 800C, stirred for two hours, and then cooled. Subsequently, the precipitate was filtered, washed with water and ethanol, and then dried by heating at 80°C under a reduced pressure. As a result, 20 g (yield: 92%) of dark green solid E6 was obtained.
90% With potassium hydroxide In ethanol at 70℃; for 3h; 1 Synthesis of Exemplary Compound A1 2.42 g (11.5 mmol) of E1 and 3.00 g (11.5 mmol) of E2 were dissolved in ethanol (40 ml), and the solution was heated to 70°. 645 mg (11.5 mmol) of potassium hydrate which was dissolved in ethanol (5 ml) was added dropwise thereto. The solution was stirred at 70° for 3 hours. After cooling, a mixed solution of water and methanol was added, filtered, and washed with methanol. By drying the filtered substance, 4.50 g (90% yield) of a black solid E3 was obtained.
88% With sodium hydroxide In ethanol; water at 60℃; for 2h; Inert atmosphere; 1.2 (2) Synthesis of Intermediate Compound M2; Under a nitrogen atmosphere, the following reagents and solvent were loaded into a 500-mL three-necked reaction vessel. 5-Bromo-acenaphthylene-1,2-dione: 15.0 g (57.5 mmol) 1,3-Diphenylpropan-2-one: 12.1 g (57.5 mmol) Ethanol: 300 mL Next, 20 mL of a 6-M aqueous solution of sodium hydroxide were dropped into the reaction solution at room temperature. After the completion of the dropping, the reaction solution was heated to 60°C, and then the reaction solution was stirred at the temperature (60°C) for about 2 hours. Next, a precipitate produced upon cooling of the reaction solution to room temperature was filtered, and then the precipitate was sequentially washed with water and ethanol. Next, the precipitate was dried by heating at 80°C under reduced pressure. Thus, 22.0 g of Intermediate Compound M2 as a dark green solid were obtained (yield: 88%).
86% With sodium hydroxide In ethanol; water at 60 - 80℃; for 2h; 1 EXAMPLE 1; Synthesis of Exemplary Compound 2; Put in 200 mL of ethanol were 10.6 g (50 mmol) of El and 10.5 g (50 mmol) of E2. After the solution was heated to 60 °C, 20 mL of 6 M aqueous sodium hydroxide solution was added dropwise. Upon completion of theaddition, the solution was heated to 80°C and was stirred for two hours. After cooling, a precipitate was filtered out, was washed with water and ethanol, and was dried by heating at 80°C under reduced pressure to yield 18.7 g of a dark green solid of E3 (yield: 86%). Next, 8.71 g (20 mmol) of E3 and 4.49 g (24 mmol) of E4 were put in 100 mL of toluene. After the solution was heated to 80°C, 2.81 g (24 mmol) of isoamyl nitrite was gradually added dropwise, and the solution was stirred at 110°C for three hours. After cooling, the solution was washed twice with 100 mL of water. The organic layer was washed with saturated saline and was dried over magnesium sulfate. The solution was thenfiltered, and the filtrate was concentrated to yield a dark brown liquid. This was purified by column chromatography (toluene/heptane, 2:3) and was recrystallized fromchloroform/methanol to yield 7.47 g of a yellow crystal of E5 (yield: 70%) .
72% With potassium hydroxide In methanol for 2h; Heating / reflux; 3 Synthesis of Intermediate 2:; To 100 mL of methanol, there were added 1,3-dipneyl-2-propanone (10 g, 48 mM) and the starting raw material 2 (12.5 g, 48 mM), followed by the gradual addition of 10 mL of a methanolic potassium hydroxide (1.7 g, 30 mM) solution and the subsequent reflux with heating for 2 hours. The solids precipitated were filtered off and washed with xylene to thus give purple solids (15 g, yield: 72%).
51% With potassium hydroxide In methanol for 4h; Inert atmosphere; Reflux; 1.1 5-bromoacenaphthylene-l, 2-dione15.6 g (60 mmol)And 13.0 g (62 mmol) of 1,3-diphenylpropan-2-one were dissolved in 300 ml of methanol and 0.2 g of potassium hydroxide was diluted with methanol, and the mixture was refluxed under nitrogen for 4 hours . After cooling, the reaction solution was filtered, washed with water and methanol, and the slurry was further purified by acetonitrile to obtain 13.4 g (51%) of a black solid.
With potassium hydroxide In methanol

  • 42
  • [ 2940-26-3 ]
  • [ 102-04-5 ]
  • [ 2423-73-6 ]
YieldReaction ConditionsOperation in experiment
With sodium hydroxide In ethanol
With sodium hydroxide In ethanol
  • 43
  • [ 50-00-0 ]
  • [ 141-43-5 ]
  • [ 102-04-5 ]
  • 3,7-bis(2-hydroxyethyl)-1,5-diphenyl-3,7-diazabicyclo<3.3.1>nonan-9-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With glacial acetic acid In ethanol; lithium hydroxide monohydrate Reflux; 1,5-Diphenyl-3,7-bis(2-hydroxyethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one (BisP1) To a mixture of 1,3-diphenylacetone (2.1 g, 0.01 mol) and ethanol (20 mL) was added ethanolamine(1.20 mL, 0.02 mol) and aqueous formaldehyde (3.24 mL, 0.04 mol). The resultant mixture was heated under reflux overnight. After this time, the reaction mixture was chilled and the resulting white precipitate collected and washed with diethyl ether to afford BisP1. Yield: 3.54 g, 93%. m.p. 182-184 C.IR (cm1): 3465, 3056, 2945, 2825, 1721, 1600, 1494, 1445, 1344, 1296, 1272, 1208, 1183, 1117, 1080, 1039,933, 836.1H NMR (CDCl3) (300 MHz): δ 2.73-2.77 (t, J = 5.0 Hz, 4H, exocyclic NCH2), 3.19-3.27 (d, J = 11.5 Hz,4H, ring CH2), 3.63-3.71 (d, J = 11.5 Hz, 4H, ring CH2), 3.74-3.78 (t, J = 5.0 Hz, 4H, CH2OH), 4.94 (br,2H, OH), 7.30-7.41 (m, 10H, aryl). 13C NMR (CDCl3) (75 MHz): δ 54.7 (CPh), 58.3 (CH2OH), 58.6 (exocyclic NCH2), 65.3 (ring CH2),127.2 (aryl), 127.3 (aryl), 128.0 (aryl), 138.1 (aryl), 209.8 (CO). Mass Spectrum (EI): m/z 380 (11%) M+, 362 (17), 307 (45), 292 (86), 276 (19), 248 (13), 234 (42), 204 (8),190 (27), 176 (24), 144 (14), 115 (57), 103 (76), 91 (68), 88 (100), 77 (33), 72 (36), 58 (70), 44 (66), 42 (58).LRMS (ESI M + 1): 381HRMS (ESI M + H) for C23H29N2O3: calculated 381.2173, found 381.2171
68% With glacial acetic acid In methanol at 90℃; for 5h; Synthesis of 3,7-bis(2-hydroxyethyl)-1,5-diphenyl-3,7-diazabicyclo[3.3.1]nonan-9-one (1). To an ice-cold solution of ethanolamine(1 eq.) in MeOH, neutralized by the slow addition of 3 mL of glacialacetic acid, was added formaldehyde (2 eq.) and 1,3-biphenyl propan-2-one (0-5 eq.). The resulting suspension was heated at 90 C under refluxfor 5 h and then cooled overnight. The solution was basified by the addition of a 20% NaOH solution; the dilution with an equal volume ofwater prompted the crystallization of the desired ligand A (Scheme 1).Yield: 68%. 1H NMR (400 MHz, CDCl3) δ 7.40 - 7.17 (m, 10H), 3.74 (t, J= 5.2 Hz, 4H), 3.66 (d, J = 11.2 Hz, 4H), 3.23 (d, J = 11.2 Hz, 4H), 2.74(t, J = 5.2 Hz, 4H).
53% In ethanol for 12h; Heating;
42% With glacial acetic acid In ethanol for 5h; Heating;

  • 44
  • [ 74-89-5 ]
  • [ 102-04-5 ]
  • [ 29639-93-8 ]
YieldReaction ConditionsOperation in experiment
With toluene-4-sulfonic acid In benzene
In toluene Heating;
With titanium(IV) isopropylate In methanol; dichloromethane for 1h; Inert atmosphere; Schlenk technique;
With titanium(IV) isopropylate In methanol; dichloromethane at 20℃; for 1h; Inert atmosphere; Schlenk technique; 6 N-Methyl-1,3-diphenylpropan-2-amine was synthesized according to the following method: At room temperature, Ti(OiPr)4 (1.5 mL, 5.2 mmol) was added to a 1,3-diphenylpropanone (commercially available, cas: 102-04-5) (1.0 g, 4.7 mmol) DCM solution (20 mL), followed by the addition of MeNH2 (3.5 mL, 7 mmol, 2M in MeOH). The reaction mixture was stirred for 1 hour and the solvent was removed. The residue was dissolved into MeOH (20 mL) and cooled to 0° C. Then NaBH4 (0.53 g, 14.1 mmol) was added to this solution and the reaction mixture was slowly warmed up to room temperature and stirred for 2 hours. Then the solvent was removed and the residue was purified by silica gel column chromatography (gradient elution: Hexanes/ EtOAc 8:1 to 1:1) to give the desired amine product as yellow oil (600 mg, 56% yield).

  • 45
  • [ 91960-97-3 ]
  • [ 102-04-5 ]
  • [ 38268-14-3 ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide In ethanol
  • 46
  • [ 76471-78-8 ]
  • [ 102-04-5 ]
  • [ 64706-24-7 ]
YieldReaction ConditionsOperation in experiment
89% With potassium hydroxide In ethanol at 80℃;
87% With potassium hydroxide In ethanol for 1h; Heating;
85% With potassium hydroxide In ethanol for 0.25h; Reflux;
80.6% With potassium hydroxide In ethanol at 90℃; for 1h;
67% With potassium hydroxide In ethanol at 85℃; for 0.666667h;
With potassium hydroxide In ethanol for 3h; Heating; Yield given;

  • 47
  • [ 867-13-0 ]
  • [ 102-04-5 ]
  • [ 198547-74-9 ]
YieldReaction ConditionsOperation in experiment
33% Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran at 0℃; Stage #2: 1,3-Diphenylpropanone In tetrahydrofuran at 20℃; 12 Step 1) Preparation of ethyl 3-benzyl-4-phenylbut-2-enoate Step 1) Preparation of ethyl 3-benzyl-4-phenylbut-2-enoate (0273) NaH (571 mg, 14.3 mmol) and anhydrous THF (20 mL) at 0° C. was added triethylphosphonoacetate (3.1 mL, 15.7 mmol) dropwise. The reaction mixture was naturally warmed to room temperature followed by a dropwise addition of 1,3 diphenyl acetone (1.9 mL, 9.5 mmol). The reaction mixture was stirred for 12 hours and then poured in water and extracted with DCM. The combined organic layer was washed with brine and dried over sodium sulfate, filtered and concentrated under reduced pressure. This was purified on ISCO chromatograph with silica to give the product as a colorless oil. (880 mg, 33%); 1H NMR (CDCl3) (400 MHz) δ 7.29 (m, 10H), 5.84 (s, 1H), 4.27 (q, 2H), 4.09 (s, 2H), 3.42 (s, 2H), 1.36 (t, 3H, J=8), 13C NMR δ 166.5, 159.8, 138.8, 137.7, 129.4, 129.1, 128.6, 128.5, 126.7, 126.4, 118.4, 59.9, 43.4, 36.8, 14.3.
With sodium hydride Ambient temperature;
Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran at 20℃; Stage #2: 1,3-Diphenylpropanone In tetrahydrofuran at 20℃;
Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran Stage #2: 1,3-Diphenylpropanone In tetrahydrofuran at 20℃;
Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran; mineral oil for 1h; Stage #2: 1,3-Diphenylpropanone In tetrahydrofuran; mineral oil

  • 48
  • [ 6921-34-2 ]
  • [ 102-04-5 ]
  • [ 6712-97-6 ]
YieldReaction ConditionsOperation in experiment
85% In diethyl ether for 12h;
85% In diethyl ether at 20℃; for 26h; Inert atmosphere; 1 Synthesis Example 1: Preparation of compound [2]The vinylbenzene-containing compound represented by the above compound [2] Preparation of intermediate compound [2-3] 381 mL (381 mmol, 1 M, in diethyl ether solution) of compound [2-2] is added to a 2 L reaction flask under a nitrogen atmosphere and stirred for 10 minutes.50 g (238 mmol) of the compound [2-1] was dissolved in anhydrous etherIt is dissolved in 500 mL and added dropwise at room temperature for 2 hours.The reaction is stirred at room temperature for 24 hours.After completion of the reaction, 350 mL of a 5% aqueous sulfuric acid solution was slowly added,Ethyl acetate was added and the mixture was vigorously stirred until the two layers were well mixed. The organic layer was separated and washed repeatedly with purified water to neutral.The organic layer was collected and the remaining water was removed with anhydrous magnesium sulfate. The reaction product was filtered, and the filtrate was concentrated under reduced pressure. The obtained product was subjected to column purification,61 g (85%) of the intermediate compound [2-3] was prepared
  • 49
  • [ 19752-61-5 ]
  • [ 102-04-5 ]
  • 2-(2,4-di-<i>tert</i>-butoxy-pyrimidin-5-yl)-1,3-diphenyl-propan-2-ol [ No CAS ]
  • 50
  • [ 151-50-8 ]
  • [ 102-04-5 ]
  • [ 23186-94-9 ]
YieldReaction ConditionsOperation in experiment
With ethanol Erwaermen unter CO2;
  • 51
  • [ 4124-41-8 ]
  • [ 102-04-5 ]
  • [ 849943-87-9 ]
YieldReaction ConditionsOperation in experiment
83% Stage #1: 1,3-Diphenylpropanone With potassium <i>tert</i>-butylate In tetrahydrofuran at -20 - 0℃; for 1.66667h; Inert atmosphere; Stage #2: p-toluenesulfonylanhydride In tetrahydrofuran at -20 - 0℃; for 6h; Inert atmosphere; 3.1 General procedure for the synthesis of alkenyl tosylate 1a-1i, 1k-1l General procedure: The solution of ketone or aldehyde (ca. 3 mmol) in THF (10 mL) was cooled to -20 °C. 1.0 M t-BuOK in THF (1.1-1.5 equiv) was added dropwise to the solution over 10 min. The mixture was warmed to 0 °C, stirred for 1.5 h, and then cooled to -20 °C. p-Toluenesulfonic anhydride (1.1-1.5 equiv) was added to the solution and the mixture was stirred for 1 h, then warmed to 0 °C, and stirred for 5 h. The mixture was diluted with EtOAc, washed with H2O and brine, dried over MgSO4, filtered, and concentrated. The obtained residue was purified by silica gel column chromatography (SiO2, hexane/EtOAc 30/1-10/1) to afford the desired alkenyl tosylate.
66% Stage #1: 1,3-Diphenylpropanone With sodium t-butanolate In 1-methyl-pyrrolidin-2-one at 20℃; for 3h; Stage #2: p-toluenesulfonylanhydride In 1-methyl-pyrrolidin-2-one at -50 - -15℃; for 2h;
58% Stage #1: 1,3-Diphenylpropanone With potassium <i>tert</i>-butylate In tetrahydrofuran at -20 - 0℃; for 1.66667h; Inert atmosphere; Stage #2: p-toluenesulfonylanhydride In tetrahydrofuran at -20 - 0℃; for 6h; Inert atmosphere;
  • 52
  • [ 181294-58-6 ]
  • [ 102-04-5 ]
  • [ 2423-73-6 ]
YieldReaction ConditionsOperation in experiment
91% With sodium ethanolate In ethanol at 80℃; for 24h;
  • 53
  • [ 492-73-9 ]
  • [ 102-04-5 ]
  • 2,5-diphenyl-3,4-bis(2-pyridyl)cyclopenta-3,4-diol-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With potassium hydroxide In ethanol for 1h;
84% With potassium hydroxide In ethanol for 1h;
  • 54
  • [ 1068-55-9 ]
  • [ 102-04-5 ]
  • [ 75245-67-9 ]
YieldReaction ConditionsOperation in experiment
97% With neodymium(III) chloride; lithium chloride In tetrahydrofuran at 0℃;
86% Stage #1: 1,3-Diphenylpropanone With lanthanium (III) chloride bis(lithium chloride) complex In tetrahydrofuran Inert atmosphere; Stage #2: isopropylmagnesium chloride In tetrahydrofuran at 0 - 25℃; Inert atmosphere;
82% Stage #1: 1,3-Diphenylpropanone In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: isopropylmagnesium chloride In tetrahydrofuran at 0℃; for 18h; Inert atmosphere;
  • 55
  • [ 7677-24-9 ]
  • [ 102-04-5 ]
  • 2-benzyl-3-phenyl-2-((trimethylsilyl)oxy)propanenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% With C29H46LaN3Si2 at 15℃; for 4h; Inert atmosphere; Glovebox; Schlenk technique; 4.5 General procedure for the intermolecular cyanosilylation of ketones General procedure: In an argon-filled glovebox, ketone 10 (16.0mmol), 0.01mol% of 3b (1mg, 1.58μmol) and TMSCN (19.0mmol) were weighed into a Schlenk tube equipped with a magnetic stirring bar. The reaction mixture was stirred at 15°C and was monitored by TLC until full consumption of the ketone. Then n-hexane (6.0mL) was added and the resulting suspension was filtered. The solvent and other volatiles of the filtrate were removed under vacuum to provide the pure product.
98% With tris(2,4,6-trimethoxyphenyl)phosphine In N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere;
92% With L-proline potassium salt at 20℃; for 24h;
With iodine In dichloromethane at 0℃; for 0.5h;
With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 0.5h;

  • 57
  • [ 84405-44-7 ]
  • [ 102-04-5 ]
  • [ 1004539-50-7 ]
YieldReaction ConditionsOperation in experiment
85% With potassium hydroxide; In methanol; for 0.5h;Heating / reflux; a) A solution of 1.40 g potassium hydroxide in 5.6 ml methanol is added to 9.15 g (25 mmol) of <strong>[84405-44-7]2,7-dibromo-phenanthrene-9,10-dione</strong> and 5.78 g (27.5 mmol) of 1 ,3-diphenyl-propan-2- <n="46"/>one in 300 ml methanol. The reaction mixture is refluxed for 30 min and cooled to 25 0C. The product is filtered off, washed with methanol and dried (yield: 1 1.5 g (85 %)).
With potassium hydroxide; In ethanol; at 50℃; for 1h; General procedure: In a 1000 ml four-necked round bottom flask, 1 equivalent of Sub 2-1 compound, 1 equivalent of propan-2-one substituted with R1 and R2 and ethanol were added and stirred. Potassium hydroxide was then added to this solution, and the mixture was stirred at 50 C for 1 hour. Thereafter, the reaction solution was cooled to room temperature, and the resulting solid was filtered, washed sufficiently with methanol, and the obtained solid was vacuum-dried to obtain Sub 2-2.
  • 58
  • [ 102-04-5 ]
  • C15H10N8O9(4-)*4Na(1+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
With nitrogen(II) oxide; sodium trimethylsilanolate In tetrahydrofuran at 20℃; for 24h; 5 This example describes a method to convert 1,3-diphenylacetone into an NO-releasing agent. Commercially available from Sigma-Aldrich is 1,3-diphenylacetone, PhCH2C(O)CH2Ph. Diphenylacetone (2.14 g, 0.010 mol) is added to a 300 ml Parr pressure vessel. Sodium trimethylsilanolate (4.28 g, 0.038 mol) is added to 40 ml of THF in a 200 ml beaker. The sodium trimethylsilanolate solution is then added to 1,3-diphenylacetone in the Parr pressure vessel with stirring. Oxygen is removed from the flask by alternating cycles (10) of inert gas pressurization and venting. The stirred solution is then exposed to 80 psi NO gas at room temperature for 24 hours. When the reaction is complete, i.e. no more NO gas was consumed, the head space is purged of NO gas and the tan solid product is filtered and washed with ether. The weight of the dried product is 5.9 g. The UV-vis spectrum of this material has a peak at 257.4 nm (10 mM NaOH) and it yields a positive Greiss reaction. Upon addition of acid to the sample, the 257.4 nm peak shifts to 243 nm. A carbonyl peak at 1714-1 cm is observed in the FT-IR (KBr pellet). The recrystallized white product is analyzed for NO release. A stock solution is made of 38.9 mg of the recrystallized white product in 50 ml of 10 mM NaOH. In a chemiluminescence reactor vessel containing 3.0 ml of pH 7.4 buffer, 1.0 ml of the product solution is injected. It is observed over a 331 minute time period that 0.0105 mg of NO is produced. This corresponds to 0.013 mg NO per mg compound.
  • 59
  • [ 596-38-3 ]
  • [ 102-04-5 ]
  • 1,3-diphenyl-1-(9-phenyl-9H-xanthen-9-yl)-propan-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With 1,1'-(ethane-1,2-diyl)dipyridinium bistribromide; acetic anhydride for 24h;
With EDPBT
  • 60
  • [ 102-04-5 ]
  • [ 620-81-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 30 percent / MeONa / methanol / 30 °C 2: SOCl2 / CHCl3 / 20 °C
  • 61
  • [ 102-04-5 ]
  • [ 4275-43-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 3 h / 165 °C 2: 6N aq. HCl / 16 h / Heating
Multi-step reaction with 2 steps 1: 175 °C 2: aqueous hydrochloric acid
  • 62
  • [ 124337-51-5 ]
  • [ 102-04-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 1.) BuLi / 1.) THF, hexane, -78 deg C, 2 h, 2.) THF, a) -78 deg C, 4 h, b) ambient temperature, 12 h 2: 63 percent / aq. HCl / tetrahydrofuran; H2O / 24 h / Ambient temperature
  • 63
  • [ 776324-96-0 ]
  • [ 102-04-5 ]
  • [ 776324-97-1 ]
YieldReaction ConditionsOperation in experiment
85.3% Stage #1: 3,5-bis(phenylethynyl)benzil; 1,3-Diphenylpropanone In isopropyl alcohol; toluene at 80℃; for 0.7h; Heating / reflux; Stage #2: With tetra(n-butyl)ammonium hydroxide In methanol; isopropyl alcohol; toluene at 80℃; for 1.68333h; 2 Example 2 Alternate Synthesis of 4- (3, 5-bis (phenylethynyl) PHENYL)-2, 3,5- triphenylcyclopentadienone Example 2 Alternate Synthesis of 4- (3, 5-bis (phenylethynyl) PHENYL)-2, 3,5- triphenylcyclopentadienone 3,5-bis (phenylethynyl) benzil (65.6 grams, 0.16 mole) prepared in the manner of Example 1, 1,3-diphenylacetone (37. 8 grams, 0. 18 mole), 2-propanol (583 milliliters) and toluene (218 milliliters), were added to a 2 liter glass four neck Morton reactor containing a magnetic stirring bar. The reactor was additionally outfitted with chilled (2°C) condenser, a thermometer with thermostatically controlled heating mantle and a subsurface tube for sparging with nitrogen. Under a nitrogen atmosphere, an addition funnel was loaded with tetrabutylammonium hydroxide (1M in methanol) (5.46 milliliters) diluted into 2-propanol (97 milliliters) which had been sparged with nitrogen. This addition funnel was then attached to the reactor under dynamic nitrogen flow. Sparing and heating of the stirred slurry commenced, and after 42 minutes, once a reflux (80°C) was achieved, a clear light yellow colored solution had formed. At this time, the sparge tube was move up out of the solution in the reactor to provide nitrogen overhead, then dropwise solution of the catalyst commenced, inducing the formation of a dark red color. After 92 minutes at reflux, 44 milliliters of the catalyst solution had been added and HPLC analysis indicated that full conversion of the 3,5- bis [phenylethynyl) benzil reactant had been achieved, with minimum formation OF COPRODUCTS. After a cumulative 101 minutes at reflux, the heating mantle was removed from the reactor, additional 2-propanol was added (413 milliliters), then an ice bath was placed under the reactor and the stirred contents were maintained therein for the next 39 minutes until a temperature of 5°C was achieved. The product was recovered via filtration through a coarse fritted glass funnel. The product cake on the funnel was washed with two portions (50 milliliters) of 2-propanol, giving a clear filtrate with the second wash. Drying in a vacuum oven to provided 79.66 grams (85.3 percent isolated yield) OF 4- (3, 5-bis (phenylethynyl)- phenyl) -2, 3,5-triphenylcyclopentadienone (UNSYMMETRICALLY substituted 3,5-AAB monomer) as a dark red purple colored crystalline product. HPLC analysis revealed the presence of the desired product at 100 area percent.
~ 100 %Chromat. With N-benzyl-trimethylammonium hydroxide In methanol; propan-1-ol; toluene at 24℃; for 16.8333h; Heating / reflux; 1 Synthesis of 4-(3,5-bis(phenylethynyl)phenyl)-2,3,5-triphenylcyclopentadienone Synthesis of 4-(3,5-bis(phenylethynyl)phenyl)-2,3,5-triphenylcyclopentadienone A portion of the 3,5-bis (phenylethynyl) benzil (10. 87 grams, 0. 0265 mole), 1,3- DIPHENYLACETONE (5. 90 grams, 0. 0281 mole), anhydrous 1-propanol (300 milliliters) and anhydrous toluene (17 milliliters), both of which had been sparged with dry nitrogen, were added under a dry nitrogen atmosphere to a predried 500 milliliter glass three neck round bottom reactor containing a predried magnetic stirring bar. The reactor was additionally outfitted with a fan cooled spiral condenser and a thermometer with thermostatically controlled heating mantle. Stirring and heating commenced, and once a refluxing clear light yellow colored solution formed, benzyltrimethylammonium hydroxide (40 percent in methanol) (0.91 gram) was added, immediately inducing a dark red color. After maintaining the reflux for 20 minutes, HPLC analysis indicated that full conversion of the 3,5-bis [phenylethynyl) benzil reactant had been achieved. After a cumulative 30 minutes of reaction, the heating mantle was removed from the reactor, and the stirred contents were maintained at 24°C for the next 16 hours. The product was recovered via filtration through a medium fritted glass funnel. The product cake on the funnel was washed with two portions (50 milliliters) of 1-propanol, then dried in a vacuum oven to provide 11.84 grams (76.4 percent isolated yield) OF 4- (3, 5- bis (phenylethynyl) phenyl) -2, 3,5-triphenylcyclopentadienone (unsymmetrically substituted 3,5- AAB monomer) as a dark red purple colored crystalline product. HPLC analysis revealed the presence of the desired product at 100 area percent. The product's identity was confirmed by H NMR and EI MS analysis.
  • 64
  • [ 13453-07-1 ]
  • [ 102-04-5 ]
  • (C6H5CH2)2AuClOH [ No CAS ]
YieldReaction ConditionsOperation in experiment
In [D3]acetonitrile Irradiation (UV/VIS); irradn. of 1,3-diphenylacetone in CD3CN in the presence of AuCl3; D2O/CDCl3 liq. extn.;
  • 65
  • [ 22516-59-2 ]
  • [ 102-04-5 ]
  • [ 1058142-60-1 ]
YieldReaction ConditionsOperation in experiment
73% With potassium hydroxide In ethanol; water; toluene at 80℃; for 0.5h; 1 The intermediate D (4.0 g, 8.7 mmol), 50 iriL of ethanol, 5 mL of toluene were charged into a reaction vessel, and 1, 3-diphenyl-2-propanone (1.8 q, 8.7 mmol) was added to the solution and then 4 mL of a 6N-KOH aqueous solution was slowly added dropwise thereto. Next, the reaction solution was heated and stirred for 30 minutes in an oil bath at 800C.Thereafter, the temperature of the reaction solution was returned to room temperature and a small amount of water was added thereto and the reaction solution was then filtered. The obtained crystal was washed sequentially with water, methanol and isopropyl ether, and then dried under reduced pressure to thereby obtain 4.0 g of an intermediate E (6.3 mmol, yield 73%) .
  • 66
  • [ 5254-01-3 ]
  • [ 102-04-5 ]
  • [ 28311-12-8 ]
YieldReaction ConditionsOperation in experiment
86% With potassium hydroxide In ethanol; water; toluene at 80℃; for 0.25h; 1 The intermediate A (10.0 g, 48 mmol), 150 mL of ethanol, 15 mL of toluene were charged into a reaction vessel, and 1, 3-diphenyl-2-propanon (10.0 g, 48 mmol) was added to the solution and then 20 ml of a 6N KOH aqueous solution was slowly added dropwise thereto. Next, the reaction solution was heated and stirred for 15 minutes in an oil bath at 80°C. The temperature of the reaction solution was returned to room temperature and a small amount of water was added thereto and the reaction solution was then filtered. The obtained crystal was washed sequentially with water, methanol and isopropyl ether, and then dried under reduced pressure to thereby obtain 15.8 g of an intermediate B (41.4 mmol, yield 86%) .
86% With potassium hydroxide In ethanol; water; toluene at 75℃; 1.1 Reagents and solvents described below were placed in a 20 mL reaction vessel. Note that XX-I is a compound synthesized according to Journal of American Chemical Society, 91, 918 (1969) . XX-I: 0.5 g (2.4 mmol) XX-2: 0.5 g (2.4 mmol)Toluene/ethanol mixed solvent (toluene: ethanol = 1:10 (weight ratio) ) : 8 mL Next, 1 mL of 6N aqueous solution of potassium hydroxide was slowly added dropwise while the reaction solution was stirred. Subsequently, the reaction solution was heated to 75°C and stirred at the temperature for 10 minutes. Then, the reaction solution was cooled to room temperature, and the precipitated crystal was filtrated. Thereafter, the crystal was sequentially washed with water and methanol, whereby 0.8 g of XX-3 (yield 86%) was obtained.
  • 67
  • [ 35578-47-3 ]
  • [ 102-04-5 ]
  • [ 1144527-63-8 ]
  • 68
  • [ 1068155-33-8 ]
  • [ 102-04-5 ]
  • [ 1068155-35-0 ]
YieldReaction ConditionsOperation in experiment
95% With potassium hydroxide In ethanol; water at 20 - 75℃; Inert atmosphere; 1.b (b) Synthesis of Intermediate Compound 4-32.01 g (7.10 mmol) of Compound 4-1, 1.50 g (7.13 mmol) of Compound 4-2, and 100 ml of ethanol were loaded into a 200-ml three-necked flask. While the mixture was stirred at room temperature in a nitrogen atmosphere, 25 ml of an aqueous solution in which 4.00 g of potassium hydroxide had been dissolved were dropped to the mixture. Next, the temperature of the resultant mixture was increased to 75°C, and then the mixture was stirred for 1 hour and 30 minutes. After the reaction liquid had been cooled, the precipitated solid was separated by filtration and dried, whereby 3.08 g of Intermediate Compound 4-3 (green powder) were obtained (95% yield)
With potassium hydroxide In ethanol; water at 75℃; 1.2 (2) Synthesis of Compound 3The following reagents and solvent were placed in a reaction vessel. Compound 2: 2 g (7.1 mmol)1, 3-Diphenylpropan-2-one: 1.5 g (7.1 mmol) Ethanol: 100 mLNext, 25 mL of 2M aqueous potassium hydroxide solution was added dropwise to the reaction solution. Then, after heating the reaction solution to 75°C, the reaction solution was stirred for 2 hours at that temperature. Subsequently, the precipitate formed when cooling the reaction solution was filtered. The precipitate was washed with ethanol and water sequentially, and dried to give 3.2 g (7.1 mmol) of Compound 3.
With potassium hydroxide 3 C- 3 can be synthesized through the following scheme: The fluorescent spectra of the toluene solution of C-3 and the spin-coated film of C-3 were measured as in Production Example 1. The fluorescent peak wavelengths are shown in Tables 1 and 2 above.
3.2 g With potassium hydroxide In ethanol; water at 75℃; for 2h; 1.2 Synthesis of Compound 3 The following reagents and solvents were charged into a reaction vessel.[0093]Compound 2: 2 g (7.1 mmol)1,3-Diphenylpropan-2-one: 1.5 g (7.1 mmol)Ethanol: 100 ml[0094]Next, 25 ml of 2 M potassium hydroxide aqueous solution was added dropwise to the reaction solution.The reaction solution was then heated to 75 ° C. and stirred at this temperature for 2 hours.Next, the precipitate formed when the reaction solution was cooled was filtered.Next, this precipitate was sequentially washed with ethanol and water, and then dried to obtain 3.2 g (7.1 mmol) of Compound 3.

  • 69
  • [ 1228304-80-0 ]
  • [ 102-04-5 ]
  • [ 1228304-81-1 ]
YieldReaction ConditionsOperation in experiment
95% Stage #1: acephenanthrylene-4,5-dione; 1,3-Diphenylpropanone In ethanol at 60℃; Stage #2: With water monomer; sodium hydroxide In ethanol at 80℃; 1 To 200 ml of ethanol, 11.6 g (50 mmol) E3 obtained as such and 10.5 g (50 mmol) of E4 were added, and the resulting mixture was heated to 600C. To the resulting mixture, 20 ml of a 5M aqueous sodium hydroxide solution was added dropwise. Upon completion of the dropwise addition, the mixture was heated to 800C, stirred for 2 hours, and cooled. Precipitates were filtered, washed with water and ethanol, and vacuum-dried under heating at 800C. As a result, 18.2 g (yield: 95%) of a dark green solid E5 was obtained.
95% With sodium hydroxide In ethanol; water monomer at 60 - 80℃; for 2h; 1-2 (1-2) Synthesis of intermediate E5Reagents and solvents described below were charged into a reactor:E3: 11.6 g (50 mmol)E4: 10.5 g (50 mmol)ethanol: 200 ml The reaction solution was heated to 60 degrees Celsius and a 5 M aqueous sodium hydroxide solution (20 ml) was added thereto dropwise. Upon completion of addition, the reaction solution was heated to 80 degrees Celsius and stirring was conducted for 2 hours at this temperature (80 degrees Celsius). Upon completion of the reaction, the reaction solution was cooled and precipitated solids were filtered and washed with water and then ethanol. Next, vacuum thermal drying was conducted at 80 degrees Celsius to obtain 18.2 g (yield: 95%) of E5 in form of dark green solids
80% With sodium hydroxide In ethanol; water monomer at 60 - 80℃; 1 To 100 ml of ethanol, 5.8 g (25 mmol) of El and 5.3 g (25 mmol) of E2 were added. The mixture was heated to 60 °C, and 10 ml of a 5M aqueous sodium hydroxide solution was added thereto dropwise. Upon completion of dropwise addition, the mixture, was heated to 80°C, stirred for 2 hours, cooled, and filtered to recover precipitates. The precipitates were washed with water and ethanol, dried at 80°C under heating at a reduced pressure. As a result, 8.1 g (yield: 80%) of dark green solid E3 was obtained.
75% With potassium hydroxide In ethanol at 70℃; for 6h; Inert atmosphere; 1.1; 8.1 (1) Synthesis of Compound G3 A 200-ml recovery flask was charged with the following reagents and solvent. (0175) Compound G1: 2.32 g (10 mmol) (0176) Compound G2: 2.10 g (10 mmol) (0177) Ethanol: 100 ml (0178) Next, the reaction solution was heated to 70° C. in a nitrogen stream, and a KOH ethanol solution was added dropwise to the reaction solution. The reaction solution was stirred at this temperature (70° C.) for 6 hours. After completion of the reaction, water was added to the product, and the precipitate was filtered. The filter cake was subjected to dispersion washing with methanol. Thus, 3.04 g (yield: 75%) of a gray compound G3 was produced. (
58% With potassium hydroxide In ethanol; toluene at 75℃; 1 To a 20-mL reaction vessel, XX-2 (1.8 g, 7.7 mmol) synthesized in accordance with Journal of American Chemical Society, 91, 918 (1969), XX-3 (1.6 g, 7.7 mmol), and a mixed solvent (110 itiL) of toluene and ethanol (toluene : ethanol = 1:10 (w/w) ) were added. A 0.5N-potassium hydroxide ethanol solution (20 mL) was gradually added dropwise to the resulting solution under stirring. The solution was heated to 75°C and stirred for three hours at the same temperature. The solution was cooled to room temperature, and precipitated crystals were filtered. The crystals were washed with water and methanol to obtain XX-4 (1.8 g, yield: 58%) .

  • 70
  • [ 35573-93-4 ]
  • [ 102-04-5 ]
  • [ 1233235-25-0 ]
YieldReaction ConditionsOperation in experiment
59% Stage #1: 3-chloro-1,1-diethoxy-propane With magnesium; ethylene dibromide In tetrahydrofuran; toluene at 15 - 25℃; Stage #2: 1,3-Diphenylpropanone In tetrahydrofuran; toluene at -30 - 0℃;
  • 71
  • [ 50-00-0 ]
  • [ 172092-33-0 ]
  • [ 102-04-5 ]
  • [ 1101929-33-2 ]
YieldReaction ConditionsOperation in experiment
62% With acetic acid In tetrahydrofuran; methanol at 65℃; for 29h; 6 Example 6 Preparation and Characterization of 1,5-diphenyl-3,7-(di[1,4,6-trimethyl-1,4-diazacycloheptan-6-yl)diazabicyclo[3.3.1]nonan-9-one (B3) Batch: Procedure: In a 100 ml flask, at 0° C., amine A1, formalin, and acetic acid are introduced in 15 ml of THF. Subsequently, at room temperature, the 1,3-diphenylpropan-2-one, in solution in 5 ml of THF, is added. The mixture is stirred at 65° C. for 29 hours. It is evaporated to dryness, then admixed with concentrated KOH solution and extracted with diethyl ether. The solvent is removed under reduced pressure. Subsequently the oily residue is taken up in a little methanol and admixed slowly and with stirring with water. A white solid is precipitated. This solid is isolated, dried, and recrystallized from methanol. Yield: 1.78 g (3.10 mmol, 62.0%).
  • 72
  • [ 10419-77-9 ]
  • [ 102-04-5 ]
  • 2-(diiodomethylene)-1,3-diphenylpropane [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: diethyl iodomethanephosphonate With potassium hexamethylsilazane In tetrahydrofuran at -78℃; for 2h; Inert atmosphere; Stage #2: 1,3-Diphenylpropanone In tetrahydrofuran at -78 - 0℃; Inert atmosphere; General procedure for gem-diiodoalkene derivatives General Procedure: An Ar-purged two-necked flask containing a solution of KHMDS (499 mg, 2.50 mmol) in THF (10 mL) was cooled to -78 °C and then a solution of (iodomethyl)phosphonic acid diethyl ester (1.39 g, 5.00 mmol) in THF (2 mL) was added. After steering at this temperature for 2 h, a solution of the ketone (2.00 mmol) in THF (1 mL) was added to the reaction mixture at -78 °C. The reaction mixture was wormed up to 0 °C and monitored by TLC or GC. When the reaction was complete, the reaction mixture was carefully diluted with water. The resulting mixture was extracted several times with EtOAc and the organic fraction was then washed with brine and dried over MgSO4. After removal of the solvent under reduced pressure, the residue was purified by chromatography on SiO2 to give the corresponding gem-diiodoalkene derivative.
  • 73
  • [ 492-73-9 ]
  • [ 102-04-5 ]
  • [ 14678-71-8 ]
YieldReaction ConditionsOperation in experiment
73.86% With potassium hydroxide In ethanol at 80℃; Inert atmosphere;
  • 74
  • [ 53348-05-3 ]
  • [ 102-04-5 ]
  • 3,6-dibromophencyclone [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With potassium hydroxide In methanol at 50℃; for 3h; 1.2 2) Synthesis of intermediate M2 In a 250 mL three-necked flask,M13.66 g, 2.3 g of dibenzyl ketone, 1.12 g of potassium hydroxide and 60 mL of solvent methanol were added successively, and the temperature was raised to 50 ° C,After 3 hours of reaction,Cooled to room temperature, filtered, the filter cake was collected and washed several times with potassium alcohol to give 4.10 g (76%) of the desired solid product.
76% With potassium hydroxide; dibenzoyl peroxide In methanol at 50℃; 1 Synthesis of Compound TM-2: Synthesis of Compound TM-2: 29.21 g TM-1, 18.44 g dibenzyl ketone,5.00g potassium hydroxide and350ml of methanol,Warm up to 50 degrees,Reaction for 5-6 hours,Cool to room temperature, filter,The solid is washed first with water and then with methanol.Dry to get 32.5g TM-2,The yield was 76%.
74% With potassium hydroxide In methanol at 20 - 80℃; for 0.0833333h; Inert atmosphere;
With potassium hydroxide In methanol for 0.5h; Reflux; Inert atmosphere;
With potassium hydroxide In ethanol at 50℃; for 1h; 4.4.1 (1) Sub 3-2 synthesis General procedure: In a 1000 ml four-neck round bottom flask, 1 equivalent of Sub 3-1 compound, 1 equivalent of propan-2-one substituted with R1, R2 and ethanol were added and stirred. Potassium hydroxide was then added to this solution, and the mixture was stirred at 50 ° C for 1 hour. Thereafter, the reaction solution was cooled to room temperature, and the resulting solid was filtered and sufficiently washed with methanol. The obtained solid was vacuum-dried to obtain Sub 3-2.

  • 75
  • [ 76895-44-8 ]
  • [ 102-04-5 ]
  • [ 1322076-40-3 ]
YieldReaction ConditionsOperation in experiment
85% With potassium hydroxide In ethanol; water at 60 - 80℃; 1 [0090] Next, 12.8 g (50 mmol) of E4 and 10.5 g (50 mmol) of E5 were put in 200 mL of ethanol, and the resulting mixture was heated to 60 degrees (Celsius). Subsequently, 20 mL of a 5 M aqueous potassium hydroxide solution was added dropwise thereto. After the dropwise addition, the reaction mixture was heated to 80 degrees (Celsius), stirring was conducted for two hours, and the reaction mixture was cooled. A precipitate was then filtered, and washed with water and ethanol. The precipitate was then dried by heating under reduced pressure at 80 degrees (Celsius). Thus, 18 g of a dark green solid E6 was obtained (yield: 85%).
85% With sodium hydroxide In ethanol; water at 60 - 80℃; 2 To 200 ml of ethanol, 13 g (50 mmol) of E8 and llg (50 mmol) of E9 were added. The mixture was heated to 60°C, and 20 ml of a 5M aqueous sodium hydroxide solution was added dropwise. Upon completion of the dropwise addition, the mixture was heated to 80°C, stirred for 2 hours, cooled, and filtered to recover precipitates. The precipitates were washed with water and ethanol and dried at 80 °C under heating at a reduced pressure. As a result, 18 g (yield: 85%) of dark green solid E6 was obtained.
With potassium hydroxide In ethanol; water; toluene at 50℃; for 1h; 1 Chem. 9][0111] Next, 3 g (11 mmol) of cyclopenta [cd] pyrene-3, 4- dione and 2.3 g (11 mmol) of 1 , 3-diphenylacetone were added to 300 mL of an ethanol/toluene (10/1) solution. Under stirring, 52 mL of 6 N aqueous potassium hydroxide was added dropwise thereto. After the completion of the dropwise addition, the mixture was heated to 50 °C, stirred for 1 hour, and cooled. The resulting precipitate was filtered, washed with water, ethanol, and isopropyl alcohol, in that order, and dried by heating under reduced pressure to give 2.85 g of 9, 11-diphenyl-lOH-pentaleno [1, 2, 3-cd] pyren-10-one as a black solid.[0112]
  • 76
  • [ 102-04-5 ]
  • [ 2519-10-0 ]
  • 77
  • [ 1384579-24-1 ]
  • [ 102-04-5 ]
  • [ 1384579-29-6 ]
YieldReaction ConditionsOperation in experiment
89% With sodium hydroxide In ethanol; water at 60 - 80℃; for 2h; 1.1 Example 1[0098] Synthesis of exemplified compound XX- 1[0099][Chem. 12][0100] (1) Synthesis of compound X3 Reagents and a solvent described below were placed in a reactor .Compound XI: 4.0 g (13 mmol)Compound X2 : 2.8 g (13 mmol)Ethanol: 65 ml[0101] Next, the reaction solution was heated to 60° C, and then 10 ml of a 6M aqueous sodium hydroxide solution was added dropwise to the solution. After the completion of addition, the reaction solution was heated to 80° C and stirred at this temperature (80°C) for 2 hours. Next, the reaction solution was cooled to produce precipitates which were then filtered off. Next, the resultant precipitates were washed in order with water and ethanol and then dried by heating at 80° C under reduced pressure to produce 6 g of compound X3 as a dark green solid (yield: 89%).
  • 78
  • [ 95-54-5 ]
  • [ 102-04-5 ]
  • [ 10173-29-2 ]
YieldReaction ConditionsOperation in experiment
78% With oxygen; triethylamine In toluene at 90℃; for 12h; 4.1. 2-Phenylquinoxaline (3aa) Typical procedure: Mix Et3N (2.53 mg, 0.025 mmol), 2-phenylacetaldehyde 1a (30 mg, 0.25 mmol), benzene-1,2-diamine 2a (32.4 mg, 0.3 mmol), in toluene (2.5 mL) under O2 (1 atm). The reaction mixture was stirred at 60 °C for 12 h. After cooling down to room temperature and concentrating in vacuum, the residue was purified by flash chromatography on a short silica gel (eluent: petroleum ether/ethyl acetate=20:1) to afford 47 mg (91%) of 3aa.
  • 79
  • [ 95-14-7 ]
  • [ 102-04-5 ]
  • [ 1394911-87-5 ]
YieldReaction ConditionsOperation in experiment
88% With iodine; sodium hydrogencarbonate In 1,2-dichloro-ethane at 80℃; for 24h; General procedure for reaction of azoles and ketones General procedure: A mixture of azole (0.2 mmol), ketone (0.3 mmol, 1.5equiv.), NaHCO3 (33.6 mg, 2.0 equiv.), I2 (101.6 mg, 2.0 equiv.), and 1,2-dichloroethane (2 mL) was stirred at 80 °C for 24 h. After cooling to room temperature, the reaction mixture was quenched with a saturated solution of Na2S2O3 (5 mL) and extracted with ethyl acetate (3x5 mL). The combined organic phases were washed with brine (10 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by flash column chromatograph, using a mixture of petroleum ether and ethyl acetate (5:1-2:1) as eluent to afford the corresponding products. The identity and purity of the products was confirmed by 1H and 13C NMR spectroscopic analysis.
  • 80
  • [ 102-04-5 ]
  • [ 58377-03-0 ]
YieldReaction ConditionsOperation in experiment
87% With hydroxylamine hydrochloride; sodium acetate; O,O-Diethyl hydrogen phosphorodithioate In 1,4-dioxane at 80 - 90℃; for 3h; Inert atmosphere; General procedure for the one-pot synthesis of thioamides 3 and 4: General procedure: to a solution of an aldehyde or a ketone (1.0 mmol) in dioxane (2 mL) was added hydroxylamine hydrochloride (1.0 mmol), sodium acetate (1.0 mmol), and O,O-diethyl dithiophosphoric acid (2) (1.0 mmol) under nitrogen atmosphere. The reaction mixture was stirred at 80-90 °C for 2-4 h, then cooled to rt, neutralized with aqueous sodium hydrogen carbonate and extracted with EtOAc (2 × 10 mL). The combined organic phase was dried over MgSO4, filtered, and evaporated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using a gradient mixture of hexane/ethyl acetate as eluent to afford the corresponding thioamide (3 or 4). All the products are known compounds and were characterized by the comparison of their mp and spectral data with those reported in the literature. 10-12
Multi-step reaction with 2 steps 1.1: sodium acetate; hydroxylamine hydrochloride / ethanol; water / Reflux 2.1: triphenylphosphine; tetrachloromethane / N,N-dimethyl-formamide / 3 h / 20 °C 2.2: 12 h / 20 °C
  • 81
  • Camphorquinone [ No CAS ]
  • [ 102-04-5 ]
  • [ 412283-33-1 ]
YieldReaction ConditionsOperation in experiment
49% With N-benzyl-trimethylammonium hydroxide In methanol; Triethylene glycol dimethyl ether at 120℃; for 24h; 4.1 Synthesis of Compound 3a (4,8,8-Trimethyl-1,3-diphenyl-4,5,6,7-tetrahydro-4,7-methano-inden-2-one) DL-camphorquinone (10 g, 60 mmol) and diphenyl acetone (12.7 g, 60 mmol) were added to triethylene glycol (50 mL), the mixture was slightly heated to be molten, benzyl trimethylammonium hydroxide in methanol (40%) (6.5 mL, 14.3 mmol) was added thereto, and the mixture was heated to 120° C. and stirred. After the reaction proceeded, the mixture turned red, and after 24 hours and thus completion of the reaction, H2O was added thereto, and the mixture was extracted from ethyl acetate. Water was removed from the solution in anhydrous MgSO4. The solvent was removed with a rotary evaporator. The residue was purified by column chromatography to obtain a red oily compound 3a (10 g, 49%). [0100] MS [M+1] 341
  • 82
  • [ 465-29-2 ]
  • [ 102-04-5 ]
  • 4,8,8-trimethyl-1,3-diphenyl-4,5,6,7-tetrahydro-4,7-methano-inden-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
49% With N-benzyl-trimethylammonium hydroxide; 2,2'-[1,2-ethanediylbis(oxy)]bisethanol In methanol at 120℃; for 24h; 4.1 (1) Synthesis of Compound 3a (4,8,8-Trimethyl-1,3-diphenyl-4,5,6,7-tetrahydro-4,7-methano-inden-2-one) DL-camphorquinone (10 g, 60 mmol) and diphenyl acetone (12.7 g, 60 mmol) were added to triethylene glycol (50 mL), the mixture was slightly heated to be molten, benzyl trimethylammonium hydroxide in methanol (40%) (6.5 mL, 14.3 mmol) was added thereto, and the mixture was heated to 120° C. and stirred. After the reaction proceeded, the mixture turned red, and after 24 hours and thus completion of the reaction, H2O was added thereto, and the mixture was extracted from ethyl acetate. Water was removed from the solution in anhydrous MgSO4. The solvent was removed with a rotary evaporator. The residue was purified by column chromatography to obtain a red oily compound 3a (10 g, 49%). [0101] MS [M+1] 341
49% With N-benzyl-trimethylammonium hydroxide In methanol; 2,2'-[1,2-ethanediylbis(oxy)]bisethanol at 120℃; for 24h; 4.1 The synthesis of compound 3a (4,8,8- trimethyl-1,3-diphenyl -4,5,6, 7-tetrahydro-4,7-methano - inden-2-one) DL- camphorquinone 10g (60mmol) and diphenyl acetone 12.7g (60 The mmol) were dissolved by heating with to triethylene glycol (50 mL), and methanol(6.5mL). Then the mixture is treated with benzyl trimethyl ammonium hydroxide(40%)(14.3 mmol) and heated at 120 °C for 24h.extracted with ethyl acetate put H2O. The solution was dried to remove moisture with anhydrous MgSO4 and the solvent removed on a rotary evaporator After, the compounds of the red oil was separated by column chromatography 3a (10g, 49%) It was obtained.
  • 83
  • [ 1558-23-2 ]
  • C24H26O3 [ No CAS ]
  • [ 86997-05-9 ]
  • [ 102-04-5 ]
YieldReaction ConditionsOperation in experiment
In chloroform at 20℃; for 1h; 5.J Example 5 TCO as a protecting group The feasibility to use the TCO group as a protective group in chemistry was studied by testing the stability of a range of TCO derivatives as model compounds under various conditions, and following the deprotection upon reaction with a tetrazine derivative under these conditions. The results in Tables 2-4 support the versatility of the TCO- based protecting group and at the same time demonstrate that in addition to aromatic and aliphatic carbamates also carbonates and aromatic and aliphatic esters and ethers are effectively cleaved from the TCO upon tetrazine reaction. In addition to amines, also hydroxy and carboxylic acids were effectively protected and subsuquently unmasked in a range of challenging conditions that are typical of standard chemical transformations. Typical example for testing the stability of a TCO compound The TCO stock solution [10 iL 25 mM; 2.5*10-7 mol) was added to a solution of the specific condition (100 μ). The mixture was stirred at the specific condition for a certain amount of time, and then the fate of the TCO compound was monitored by HPLC- MS/PDA analysis and/or GC-MS analysis, and an estimation of its stability was made. Typical example for testing the feasibility of the deprotection The TCO stock solution (10 μ, 25 mM in acetonitrile; 2.5*10-7 mol) was added to a solution of the specific condition (100 i ). A solution of 3,6-dimethyl-l,2,4,5-tetrazine (8, 20 uL 25 mM in acetonitrile; 5.0*10"7 mol) was added, and the mixture was stirred at the specific condition for a certain amount of time. The reaction was monitored by HPLC-MS/PDA analysis and/or GC-MS analysis, and the percentage of deprotection was estimated. Conditions: A) in acetonitrile with 5 equivalents of pyridine per TCO at 20°C B) in acetonitrile with 5 equivalents of DIPEA per TCO at 20°C C) in acetonitrile with 5 equivalents of piperidine per TCO at 20°C D) in acetonitrile with 5 equivalents of n-butylamine per TCO at 20°C E) in acetonitrile with 5 equivalents of 2-mercaptoethanol per TCO at 20°C F) in tetrahydrofuran with 5 equivalents of triphenylphosphine per TCO at 20°C G) in acetonitrile with 5 equivalents of DCC per TCO at 20°C H) in acetonitrile with 5 equivalents of PyBOP per TCO at 20°C I) in acetonitrile with 1 v% of formic acid at 20°C J) in chloroform at 20°C K) in chloroform with 1 v% of formic acid at 20°C L) in chloroform with 1 v% of trifluoroacetic acid at 20°C M) in chloroform with 10 v% of trifluoroacetic acid at 20°C N) in chloroform with 33 v% of trifluoroacetic acid at 20°C Z) in 25% acetonitrile in water at 20°C Table 2 TCO Condition Stability of Deprotection Deprotected TCO f%l product O A] for 1 h stable 87 NH2 B] for 1 h stable 58 C] for 1 h stable 48 D) for 1 h stable 47 axial isomer E] for 1 h stable 67 F] for 1 h stable 75 G) for 1 h stable 74 H) for 1 h stable 74 I] for 1 h stable 93 J] for 1 h stable 73 K) for 1 h stable 98 L] for 1 h stable 99 M) for 1 h stable 99 Z] for 1 h stable 85 "N A] for 1 h stable 68 B) for 1 h ca. 2% 83 H0K N°2 hydrolysis axial isomer G] for 1 h stable 89 I] for 1 h stable 95 Z] for 1 h stable 80 Z] for 1 h stable 66 H° N°2 equatorial isomer P A] for 1 h stable 42 X B] for 1 h stable 92 H0→O G] for 1 h stable 80 axial isomer I] for 1 h stable 92 Z] for 1 h stable 87 P Z) for 1 h stable 72 H0→O equatorial isomer Table 3 Table 4 *): study is performed at 20°C, unless stated otherwise
  • 84
  • [ 93301-76-9 ]
  • [ 103-80-0 ]
  • [ 86997-05-9 ]
  • [ 102-04-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: dmap / dichloromethane / 96 h / Cooling with ice 2: chloroform / 1 h / 20 °C
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