Name: 2510-01-2|2-(2,3-Dihydro-1H-inden-1-ylidene)malononitrile|97%
Brand: Ambeed
SKU: A197541
Price: 8.0 USD
Availability: InStock
Rating: 91 (26 reviews)

1
[ 2510-01-2 ]
[ 58787-18-1 ]

Yield	Reaction Conditions	Operation in experiment
67%	With formic acid; palladium diacetate at 20℃; for 4h;	General procedure for synthesis of monoamides 2 General procedure: A mixture of 2-substituted methylenemalononitrile (0.325 mmol) and Pd(OAc)2 (1.82mg, 2.5 mol%) in HCOOH (2.0 mL) was stirred at room temperature for 10 min and then diluted with water. The mixture was saturated with sodium carbonate until the pH=7-8, followed by extraction with dichloromethane (3*20 mL). The combined organic phase was washed with saturated brine (320 mL), dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by flash chromatography (silica gel, petroleum ether:ethyl acetate = 2:1) to give (E)- Monoamides.
	With PPA; water

Reference： [1]Liu, Yingtian; Dang, Xinxin; He, Yu; Bai, Hudong; Chen, Xuehong; Li, Jun-Long; Fan, Junting; Jiang, Hezhong; Li, Jiahong [Synthetic Communications, 2019, vol. 49, # 5, p. 662 - 671]
[2]Campaigne,E.; Ellis,R.L. [Journal of Organic Chemistry, 1967, vol. 32, p. 2372 - 2375]

2
[ 83-33-0 ]
[ 109-77-3 ]
[ 2510-01-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With anhydrous Sodium acetate In ethanol at 20℃;
83%	With anhydrous ammonium acetate; glacial acetic acid In benzene for 6h; Heating;
82%	With anhydrous ammonium acetate; glacial acetic acid In benzene

72%
40%	With anhydrous ammonium acetate; glacial acetic acid In toluene Heating;
	With ammonium acetate; glacial acetic acid
	With piperidine
	With ammonium acetate; glacial acetic acid In benzene for 24h; Heating;
	Alkaline conditions; Inert atmosphere; Glovebox;
	With ammonium acetate; glacial acetic acid In toluene for 12h; Reflux;	4.2 General procedure for the preparation of perfluoroalkylated fluorenes 4 General procedure: The suspension of indenones 1 (1.0mmol), malononitrile2 (1.0mmol), HOAc (0.1 equiv.) and NH4OAc (0.2 equiv.) was stirred in refluxing toluene (5mL) for 12h. When the resultant mixture was cooled to room temperature, methyl perfluoroalk-2-ynoates 3 (1.3 equiv.) and K2CO3 (1.5 equiv.) were added and continued to be stirred at 80°C for another 6h. Then the solvent was removed under reduced pressure and the residue was subjected to column chromatography on silica gel, eluting with petroleum ether/ethyl acetate 20:1 to 10:1 to afford the desired products 4.
	With triethylamine In ethanol at 20℃; for 2h;	General procedure for synthesis of methylenemalononitriles General procedure: Malononitrile (9.5 mmol) and the aldehyde (9.5 mmol) were dissolved in 5 mL of EtOH in a 50 mL flask, followed by adding one drop of triethylamine. After stirring at room temperature for 2 h, filtrate the solid to give the crude products. Further purification was completed by flash chromatography.
	With ammonium acetate; glacial acetic acid In toluene Reflux; Dean-Stark;
	With anhydrous Sodium acetate In ethanol at 20℃;
	With anhydrous Sodium acetate In ethanol

Reference： [1]Chen, Xiao-Hang; Zhao, Zujin; Liu, Yang; Lu, Ping; Wang, Yan-Guang [Chemistry Letters, 2008, vol. 37, # 6, p. 570 - 571]
[2]Hegab, Mohamed I.; Hassan, Nasser A.; Rashad, Aymn E.; Fahmy, Afaf A.; Abdel-Megeid, Farouk M. E. [Phosphorus, Sulfur and Silicon and the Related Elements, 2007, vol. 182, # 7, p. 1535 - 1556]
[3]Cookson, Richard C.; Sadler, David E.; Salisbury, Kingsley [Journal of the Chemical Society. Perkin transactions II, 1981, p. 774 - 782]
[4]Elinson; Fedukovich; Vereshchagin; Dorofeev; Dmitriev; Nikishin [Russian Chemical Bulletin, 2003, vol. 52, # 10, p. 2235 - 2240]
[5]Xue, Dong; Chen, Ying-Chun; Cui, Xin; Wang, Qi-Wei; Zhu, Jin; Deng, Jin-Gen [Journal of Organic Chemistry, 2005, vol. 70, # 9, p. 3584 - 3591]
[6]Hart,H.; Kim,Y.C. [Journal of Organic Chemistry, 1966, vol. 31, p. 2784 - 2789]
[7]Anderson,D.M.W. et al. [Journal of the Chemical Society, 1961, p. 4705 - 4711]
[8]Aadil, M.; Kirsch, G. [Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 82, # 1-4, p. 91 - 98]
[9]Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing [Journal of Organic Chemistry, 2013, vol. 78, # 14, p. 7154 - 7168]
[10]Sun, Zhenhua; Huang, Qi; Han, Jing; He, Weimin; Chen, Jie; Xu, Yuchen; Deng, Hongmei; Shao, Min; Zhang, Hui; Cao, Weiguo [Tetrahedron, 2018, vol. 74, # 16, p. 2073 - 2078]
[11]Liu, Yingtian; Dang, Xinxin; He, Yu; Bai, Hudong; Chen, Xuehong; Li, Jun-Long; Fan, Junting; Jiang, Hezhong; Li, Jiahong [Synthetic Communications, 2019, vol. 49, # 5, p. 662 - 671]
[12]Chen, Hui; Zhao, Sihan; Cheng, Shaobing; Dai, Xingjie; Xu, Xiaoying; Yuan, Weicheng; Zhang, Xiaomei [Journal of Heterocyclic Chemistry, 2019, vol. 56, # 5, p. 1672 - 1683]
[13]Yahya, Mohamed; Çakmaz, Deniz; Achelle, Sylvain; le Gall, Estelle; Şahin, Ertan; Seferoğlu, Zeynel [Journal of Photochemistry and Photobiology A: Chemistry, 2021, vol. 416]
[14]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY; UNIVERSITY OF CALIFORNIA; 1200 PHARMA LLC - WO2022/115439, 2022, A1 Location in patent: Page/Page column 173

3
[ 2510-01-2 ]
[ 177896-09-2 ]
[(1-dicyanomethylene-indan-2-yl)-phenyl-methyl]-carbamic acid <i>tert</i>-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With 1-{(1R,2R)-2-(dimethylamino)cyclohexyl}-3-cyclohexylthiourea; 4 A molecular sieve In toluene at 20℃;

Reference： [1]Liu, Tian-Yu; Cui, Hai-Lei; Long, Jun; Li, Bang-Jing; Wu, Yong; Ding, Li-Sheng; Chen, Ying-Chun [Journal of the American Chemical Society, 2007, vol. 129, # 7, p. 1878 - 1879]

4
[ 2510-01-2 ]
[ 1044509-91-2 ]
[ 1044509-95-6 ]

Yield	Reaction Conditions	Operation in experiment
60%	With piperidine In N,N-dimethyl-formamide at 85℃;
60%	With piperidine In N,N-dimethyl-formamide at 85℃; for 4h; Inert atmosphere;

Reference： [1]Chen, Xiao-Hang; Zhao, Zujin; Liu, Yang; Lu, Ping; Wang, Yan-Guang [Chemistry Letters, 2008, vol. 37, # 6, p. 570 - 571]
[2]Chen, Yiyang; Lu, Ping; Wang, Yanguang [Organic Letters, 2019, vol. 21, # 7, p. 2130 - 2133]

5
[ 2510-01-2 ]
[ 40703-88-6 ]
[ 1044509-93-4 ]

Yield	Reaction Conditions	Operation in experiment
62%	With piperidine In N,N-dimethyl-formamide at 85℃;
62%	With piperidine In N,N-dimethyl-formamide at 85℃; for 4h; Inert atmosphere;

Reference： [1]Chen, Xiao-Hang; Zhao, Zujin; Liu, Yang; Lu, Ping; Wang, Yan-Guang [Chemistry Letters, 2008, vol. 37, # 6, p. 570 - 571]
[2]Chen, Yiyang; Lu, Ping; Wang, Yanguang [Organic Letters, 2019, vol. 21, # 7, p. 2130 - 2133]

6
[ 2510-01-2 ]
[ 1038619-07-6 ]
[ 1393333-80-6 ]

Yield	Reaction Conditions	Operation in experiment
73%	Stage #1: 1-(dicyanomethylene)indan; C₁₁H₁₇NO₆ With triethylamine In acetonitrile at 20℃; Cooling with ice; Stage #2: With triethylamine In acetonitrile for 18h; Reflux; Stage #3: With hydrogenchloride In water; acetonitrile	4.2. General procedure for the preparation of anilines 6 General procedure: Triethylamine (TEA, 0.15 mmol) was added to a stirred, cooled (ice-water) solution of ylidene malonitrile derivative 4 (1 mmol) and β-nitroacrylate 5 (1 mmol) in acetonitrile (2.5 mL). The mixture was allowed to reach room temperature and left for the appropriate time (Table 2). Then, further 2.5 mL of MeCN and TEA (0.85 mmol) were added and the mixture was gradually heated and refluxed for the appropriate time (Table 2). After cooling, the reaction mixture was quenched with 2 M HCl (10 mL), extracted with EtOAc and the organic layer dried over Na2SO4. After removal of the solvent at reduced pressure, the crude product was purified by flash chromatography column (hexane/EtOAc), allowing the pure aniline 6.

Reference： [1]Location in patent: experimental part Gabrielli, Serena; Palmieri, Alessandro; Panmand, Deepak S.; Lanari, Daniela; Vaccaro, Luigi; Ballini, Roberto [Tetrahedron, 2012, vol. 68, # 39, p. 8231 - 8235]

7
[ 2510-01-2 ]
[ 1393333-69-1 ]
[ 1393333-84-0 ]

Yield	Reaction Conditions	Operation in experiment
63%	Stage #1: 1-(dicyanomethylene)indan; C₉H₁₃NO₆ With triethylamine In acetonitrile at 20℃; Cooling with ice; Stage #2: With triethylamine In acetonitrile for 18h; Reflux; Stage #3: With hydrogenchloride In water; acetonitrile	4.2. General procedure for the preparation of anilines 6 General procedure: Triethylamine (TEA, 0.15 mmol) was added to a stirred, cooled (ice-water) solution of ylidene malonitrile derivative 4 (1 mmol) and β-nitroacrylate 5 (1 mmol) in acetonitrile (2.5 mL). The mixture was allowed to reach room temperature and left for the appropriate time (Table 2). Then, further 2.5 mL of MeCN and TEA (0.85 mmol) were added and the mixture was gradually heated and refluxed for the appropriate time (Table 2). After cooling, the reaction mixture was quenched with 2 M HCl (10 mL), extracted with EtOAc and the organic layer dried over Na2SO4. After removal of the solvent at reduced pressure, the crude product was purified by flash chromatography column (hexane/EtOAc), allowing the pure aniline 6.

Reference： [1]Location in patent: experimental part Gabrielli, Serena; Palmieri, Alessandro; Panmand, Deepak S.; Lanari, Daniela; Vaccaro, Luigi; Ballini, Roberto [Tetrahedron, 2012, vol. 68, # 39, p. 8231 - 8235]

8
[ 2510-01-2 ]
ethyl 3-nitrobut-2-enoate [ No CAS ]
[ 1393333-82-8 ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 1-(dicyanomethylene)indan; ethyl 3-nitrobut-2-enoate With triethylamine In acetonitrile at 20℃; Cooling with ice; Stage #2: With triethylamine In acetonitrile for 18h; Reflux; Stage #3: With hydrogenchloride In water; acetonitrile	4.2. General procedure for the preparation of anilines 6 General procedure: Triethylamine (TEA, 0.15 mmol) was added to a stirred, cooled (ice-water) solution of ylidene malonitrile derivative 4 (1 mmol) and β-nitroacrylate 5 (1 mmol) in acetonitrile (2.5 mL). The mixture was allowed to reach room temperature and left for the appropriate time (Table 2). Then, further 2.5 mL of MeCN and TEA (0.85 mmol) were added and the mixture was gradually heated and refluxed for the appropriate time (Table 2). After cooling, the reaction mixture was quenched with 2 M HCl (10 mL), extracted with EtOAc and the organic layer dried over Na2SO4. After removal of the solvent at reduced pressure, the crude product was purified by flash chromatography column (hexane/EtOAc), allowing the pure aniline 6.

Reference： [1]Location in patent: experimental part Gabrielli, Serena; Palmieri, Alessandro; Panmand, Deepak S.; Lanari, Daniela; Vaccaro, Luigi; Ballini, Roberto [Tetrahedron, 2012, vol. 68, # 39, p. 8231 - 8235]

9
[ 2510-01-2 ]
ethyl 3-nitropent-2-enoate [ No CAS ]
[ 1393333-78-2 ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 1-(dicyanomethylene)indan; ethyl 3-nitropent-2-enoate With triethylamine In acetonitrile at 20℃; Cooling with ice; Stage #2: With triethylamine In acetonitrile for 18h; Reflux; Stage #3: With hydrogenchloride In water; acetonitrile	4.2. General procedure for the preparation of anilines 6 General procedure: Triethylamine (TEA, 0.15 mmol) was added to a stirred, cooled (ice-water) solution of ylidene malonitrile derivative 4 (1 mmol) and β-nitroacrylate 5 (1 mmol) in acetonitrile (2.5 mL). The mixture was allowed to reach room temperature and left for the appropriate time (Table 2). Then, further 2.5 mL of MeCN and TEA (0.85 mmol) were added and the mixture was gradually heated and refluxed for the appropriate time (Table 2). After cooling, the reaction mixture was quenched with 2 M HCl (10 mL), extracted with EtOAc and the organic layer dried over Na2SO4. After removal of the solvent at reduced pressure, the crude product was purified by flash chromatography column (hexane/EtOAc), allowing the pure aniline 6.

Reference： [1]Location in patent: experimental part Gabrielli, Serena; Palmieri, Alessandro; Panmand, Deepak S.; Lanari, Daniela; Vaccaro, Luigi; Ballini, Roberto [Tetrahedron, 2012, vol. 68, # 39, p. 8231 - 8235]

10
[ 2510-01-2 ]
[ 5147-80-8 ]
2,5-diamino-11H-indeno-[2,1-c]-pyrazolo[1,5-α]pyridine-1,6-dicarbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%		General procedure: To a solution of α,α-dicyanoolefin 1 (1 mmol) and ketenedithioacetal 2 (1 mmol) in EtOH (3 mL) was added Et3N (1mmol), and the solution was stirred for 30 min at r.t. Then,excess hydrazine was added to mixture. Upon completion(2 h, monitoring by TLC), the mixture was filtered and theprecipitate washed with EtOH (2 × 4 mL) to afford the pureproducts 3a,b,e,f and 4a-d.

Reference： [1]Synlett,2014,vol. 25,p. 2475 - 2479

11
[ 2510-01-2 ]
[ 762-42-5 ]
dimethyl 3-amino-4-cyano-9H-fluorene-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium carbonate In ethanol for 24h; Reflux;	General procedure for preparation dialkyl3-amino-4-cyano-9H-fluorene-1,2-dicarboxylates (3) General procedure: A mixture of 2-(2,3-dihydro-1H-inden-1-ylidene)malononitrile(1 mmol) and dialkylacetylene dicarboxylate(1 mmol) in refluxing ethanol (3 mL) was stirred for 48 h.After completion of the reaction (confirmed by TLC), thereaction mixture was cooled to room temperature. Then,the yellow precipitate was filtered and washed with ethanol(10 mL) to afford the pure products.

Reference： [1]Ahadi, Somayeh; Zolghadr, Mahdi; Shakibaei, Ghazaleh Imani; Bazgir, Ayoob [Journal of the Iranian Chemical Society, 2016, vol. 13, # 2, p. 369 - 375]

12
[ 2510-01-2 ]
[ 762-21-0 ]
diethyl 3-amino-4-cyano-9H-fluorene-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium carbonate In ethanol for 24h; Reflux;	General procedure for preparation dialkyl3-amino-4-cyano-9H-fluorene-1,2-dicarboxylates (3) General procedure: A mixture of 2-(2,3-dihydro-1H-inden-1-ylidene)malononitrile(1 mmol) and dialkylacetylene dicarboxylate(1 mmol) in refluxing ethanol (3 mL) was stirred for 48 h.After completion of the reaction (confirmed by TLC), thereaction mixture was cooled to room temperature. Then,the yellow precipitate was filtered and washed with ethanol(10 mL) to afford the pure products.

Reference： [1]Ahadi, Somayeh; Zolghadr, Mahdi; Shakibaei, Ghazaleh Imani; Bazgir, Ayoob [Journal of the Iranian Chemical Society, 2016, vol. 13, # 2, p. 369 - 375]

13
[ 2510-01-2 ]
[ 66086-33-7 ]
di-tert-butyl 3-amino-4-cyano-9H-fluorene-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With potassium carbonate In ethanol for 24h; Reflux;	General procedure for preparation dialkyl3-amino-4-cyano-9H-fluorene-1,2-dicarboxylates (3) General procedure: A mixture of 2-(2,3-dihydro-1H-inden-1-ylidene)malononitrile(1 mmol) and dialkylacetylene dicarboxylate(1 mmol) in refluxing ethanol (3 mL) was stirred for 48 h.After completion of the reaction (confirmed by TLC), thereaction mixture was cooled to room temperature. Then,the yellow precipitate was filtered and washed with ethanol(10 mL) to afford the pure products.

Reference： [1]Ahadi, Somayeh; Zolghadr, Mahdi; Shakibaei, Ghazaleh Imani; Bazgir, Ayoob [Journal of the Iranian Chemical Society, 2016, vol. 13, # 2, p. 369 - 375]

14
[ 872-85-5 ]
[ 2510-01-2 ]
[ 109-77-3 ]
3-amino-1-(4-pyridyl)-2,4-dicyanofluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With pyrrolidine In acetonitrile at 20℃; for 0.25h;	General procedure for the synthesis of compounds 2-5 General procedure: 1-Dicyanomethyleneindane (180mg, 1mmol), appropriate heteroaryl aldehyde (1.5mmol) and malononitrile (1.5mmol, 99mg) were dissolved in acetonitrile (15mL). Then, slowly, pyrrolidine (1.2mmol, 85μL) was added to the solution and the mixture stirred for 15minat room temperature. The obtained crude product was collected by filtration and recrystallized from ethanol.
	With pyrrolidine In acetonitrile at 20℃; for 0.25h;	General procedure for the synthesis of DSAF 1-4 General procedure: 1-Dicyanomethyleneindane (180mg, 1mmol), appropriate hetaryl aldehyde (1.5mmol) and malononitrile (1.5mmol, 99mg) were dissolved in acetonitrile (15mL). Then, slowly, pyrrolidine (1.2mmol, 85μL) was added to the solution and the mixture stirred for 15min at room temperature. The obtained crude product was collected by filtration and recrystallized from ethanol

Reference： [1]Yalçin, Ergin; Matković, Marija; Jukić, Marijana; Obrovac, Ljubica Glavaš; Piantanida, Ivo; Seferoğlu, Zeynel [Tetrahedron, 2018, vol. 74, # 5, p. 535 - 543]
[2]Yalçin; Duyar; Çakmaz; Şahin; Seferoğlu, Zeynel [Tetrahedron, 2019, vol. 75, # 35]

15
[ 500-22-1 ]
[ 2510-01-2 ]
[ 109-77-3 ]
3-amino-1-(3-pyridyl)-2,4-dicyanofluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With pyrrolidine In acetonitrile at 20℃; for 0.25h;	General procedure for the synthesis of compounds 2-5 General procedure: 1-Dicyanomethyleneindane (180mg, 1mmol), appropriate heteroaryl aldehyde (1.5mmol) and malononitrile (1.5mmol, 99mg) were dissolved in acetonitrile (15mL). Then, slowly, pyrrolidine (1.2mmol, 85μL) was added to the solution and the mixture stirred for 15minat room temperature. The obtained crude product was collected by filtration and recrystallized from ethanol.
	With pyrrolidine In acetonitrile at 20℃; for 0.25h;	General procedure for the synthesis of DSAF 1-4 General procedure: 1-Dicyanomethyleneindane (180mg, 1mmol), appropriate hetaryl aldehyde (1.5mmol) and malononitrile (1.5mmol, 99mg) were dissolved in acetonitrile (15mL). Then, slowly, pyrrolidine (1.2mmol, 85μL) was added to the solution and the mixture stirred for 15min at room temperature. The obtained crude product was collected by filtration and recrystallized from ethanol

Reference： [1]Yalçin, Ergin; Matković, Marija; Jukić, Marijana; Obrovac, Ljubica Glavaš; Piantanida, Ivo; Seferoğlu, Zeynel [Tetrahedron, 2018, vol. 74, # 5, p. 535 - 543]
[2]Yalçin; Duyar; Çakmaz; Şahin; Seferoğlu, Zeynel [Tetrahedron, 2019, vol. 75, # 35]

16
[ 1121-60-4 ]
[ 2510-01-2 ]
[ 109-77-3 ]
3-amino-1-(2-pyridyl)-2,4-dicyanofluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With pyrrolidine In acetonitrile at 20℃; for 0.25h;	General procedure for the synthesis of compounds 2-5 General procedure: 1-Dicyanomethyleneindane (180mg, 1mmol), appropriate heteroaryl aldehyde (1.5mmol) and malononitrile (1.5mmol, 99mg) were dissolved in acetonitrile (15mL). Then, slowly, pyrrolidine (1.2mmol, 85μL) was added to the solution and the mixture stirred for 15minat room temperature. The obtained crude product was collected by filtration and recrystallized from ethanol.
	With pyrrolidine In acetonitrile at 20℃; for 0.25h;	General procedure for the synthesis of DSAF 1-4 General procedure: 1-Dicyanomethyleneindane (180mg, 1mmol), appropriate hetaryl aldehyde (1.5mmol) and malononitrile (1.5mmol, 99mg) were dissolved in acetonitrile (15mL). Then, slowly, pyrrolidine (1.2mmol, 85μL) was added to the solution and the mixture stirred for 15min at room temperature. The obtained crude product was collected by filtration and recrystallized from ethanol

Reference： [1]Yalçin, Ergin; Matković, Marija; Jukić, Marijana; Obrovac, Ljubica Glavaš; Piantanida, Ivo; Seferoğlu, Zeynel [Tetrahedron, 2018, vol. 74, # 5, p. 535 - 543]
[2]Yalçin; Duyar; Çakmaz; Şahin; Seferoğlu, Zeynel [Tetrahedron, 2019, vol. 75, # 35]

17
[ 98-03-3 ]
[ 2510-01-2 ]
[ 109-77-3 ]
3-amino-1-(2-thienyl)-2,4-dicyanofluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With pyrrolidine In acetonitrile at 20℃; for 0.25h;	General procedure for the synthesis of compounds 2-5 General procedure: 1-Dicyanomethyleneindane (180mg, 1mmol), appropriate heteroaryl aldehyde (1.5mmol) and malononitrile (1.5mmol, 99mg) were dissolved in acetonitrile (15mL). Then, slowly, pyrrolidine (1.2mmol, 85μL) was added to the solution and the mixture stirred for 15minat room temperature. The obtained crude product was collected by filtration and recrystallized from ethanol. 4.3.1 3-Amino-1-(2-thienyl)-2,4-dicyanofluorene (2) (0028) A light yellow solid. (266mg, 85%) m.p.: 303-304°C; IR (KBr) υmax/cm-l: 3435, 3355, 3224, 3108, 2903, 2212, 1651, 1634, 735. 1H NMR (300MHz. DMSO-d6, 25°C): δH=8.35 (m, 1H). 7.90 (dd, J=5.07, 1.15Hz, 1H), 7.65 (dd, J=7.45, 4.52Hz, 1H), 7.50 (m, 3H), 7.25 (dd, J=5.05, 3.62Hz, 1H), 6.9 (s, br, 2H), 3.85 (s, 2H) ppm. 13C-APT (75Hz, DMSO-d6): δC=154.2, 147.3, 146.5, 139.4, 137.9, 136.3, 131.2, 130.4, 129.6, 128.2, 127.9, 126.1, 122.5, 116.9, 116.2, 94.6, 88.03, 36.6ppm. HRMS (ESI-CH3CN) calcd. for C19H13N3S [M+H]+ 312.0595; found 312.0583
	With pyrrolidine In acetonitrile at 20℃; for 0.25h;	General procedure for the synthesis of DSAF 1-4 General procedure: 1-Dicyanomethyleneindane (180mg, 1mmol), appropriate hetaryl aldehyde (1.5mmol) and malononitrile (1.5mmol, 99mg) were dissolved in acetonitrile (15mL). Then, slowly, pyrrolidine (1.2mmol, 85μL) was added to the solution and the mixture stirred for 15min at room temperature. The obtained crude product was collected by filtration and recrystallized from ethanol

Reference： [1]Yalçin, Ergin; Matković, Marija; Jukić, Marijana; Obrovac, Ljubica Glavaš; Piantanida, Ivo; Seferoğlu, Zeynel [Tetrahedron, 2018, vol. 74, # 5, p. 535 - 543]
[2]Yalçin; Duyar; Çakmaz; Şahin; Seferoğlu, Zeynel [Tetrahedron, 2019, vol. 75, # 35]

18
[ 98-03-3 ]
[ 2510-01-2 ]
(E)-2-(2-(thiophen-2-ylmethylene)-2,3-dihydro-1H-inden-1-ylidene)malononitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With morpholine In toluene Reflux;	Synthesis of compound 1 1-Dicyanomethyleneindane (180mg, 1mmol) and 2-thiophenecarboxaldehyde (1mmol, 95μL) were dissolved in fresh distilled toluene (20mL). A few drops of morpholine as a catalyst was added, and the mixture was stirred under reflux, while the reaction monitored by TLC. After cooling to room temperature the precipitate was filtered off and then recrystallized using toluene to obtain a pure brown compound. 4.2.1 (E)-2-(2-(Thiophen-2-ylmethylene)-2,3-dihydro-1H-inden-1-ylidene)malononitrile (1) (0026) Brown compound. (178mg, 65%) m.p.: 220-221°C; IR (KBr) υmax/cm-l: 3118, 2910, 2210, 1595-1571, 768. 1H NMR (300MHz. DMSO-d6. 25°C): δH=8.56 (s, 1H), 8.43 (d, J=8.10Hz, 1H), 8.12 (d, J=4.89, 1H), 7.72 (d, J=4.22Hz, 2H), 7.68 (d, J=3.51, 1H), 7.60 (m, 1H), 7.65 (dd, J=5.08, 3.73Hz, 1H), 4.40 (s, 2H) ppm. 13C-APT (75Hz, DMSO-d6): δC=166.3, 147.7, 139.3, 136.9, 135.4, 135.2, 134.9, 134.5, 129.8, 129.5, 128.7, 126.6, 125.2, 116.2, 115.8, 37.4ppm. HRMS (ESI-CH3CN) calcd. for C17H12N2S [M+H]+ 275.0646; found 275.0643.

Reference： [1]Yalçin, Ergin; Matković, Marija; Jukić, Marijana; Obrovac, Ljubica Glavaš; Piantanida, Ivo; Seferoğlu, Zeynel [Tetrahedron, 2018, vol. 74, # 5, p. 535 - 543]

19
[ 2510-01-2 ]
[ 70577-95-6 ]
methyl 3-amino-4-cyano-1-(trifluoromethyl)-9H-fluorene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In toluene at 80℃; for 6h;	4.2 General procedure for the preparation of perfluoroalkylated fluorenes 4 General procedure: The suspension of indenones 1 (1.0mmol), malononitrile2 (1.0mmol), HOAc (0.1 equiv.) and NH4OAc (0.2 equiv.) was stirred in refluxing toluene (5mL) for 12h. When the resultant mixture was cooled to room temperature, methyl perfluoroalk-2-ynoates 3 (1.3 equiv.) and K2CO3 (1.5 equiv.) were added and continued to be stirred at 80°C for another 6h. Then the solvent was removed under reduced pressure and the residue was subjected to column chromatography on silica gel, eluting with petroleum ether/ethyl acetate 20:1 to 10:1 to afford the desired products 4. 4.2.1 Methyl 3-amino-4-cyano-1-(trifluoromethyl)-9H-fluorene-2-carboxylate (4a). Yellow solid (82%). m.p.: 161.3-163.7°C. 1H NMR (500MHz, DMSO-d6) δ: 3.85 (s, 3H), 3.86 (s, 2H), 6.26 (brs, 2H), 7.39-7.43 (m, 2H), 7.55-7.57 (m, 1H), 8.16-8.17 (m, 1H) ppm. 13C NMR (125MHz, DMSO-d6) δ: 35.9, 53.8, 91.9, 114.9, 116.0, 121.8, 123.7 (q, 1JC-F=274.0Hz, CF3), 125.7, 127.5 (q, 2JC-F=31.4Hz), 127.9, 128.6, 130.0, 137.0, 145.4, 145.8, 148.8, 166.6ppm. 19F NMR (470MHz, DMSO-d6) δ: -57.8 (s, CF3) ppm. IR (KBr): υ 3360, 2949, 2220, 1708, 1622, 1426, 1274, 1233, 1160, 1128, 754cm-1. MS (EI) m/z (%): 332 [M]+. HRMS (ESI) calcd. for C17H11F3N2O2 [(M+H)]+: 333.0852. found: 333.0846.

Reference： [1]Sun, Zhenhua; Huang, Qi; Han, Jing; He, Weimin; Chen, Jie; Xu, Yuchen; Deng, Hongmei; Shao, Min; Zhang, Hui; Cao, Weiguo [Tetrahedron, 2018, vol. 74, # 16, p. 2073 - 2078]

20
[ 2510-01-2 ]
[ 104721-32-6 ]
methyl 3-amino-4-cyano-1-(pentafluoroethyl)-9H-fluorene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In toluene at 80℃; for 6h;	4.2 General procedure for the preparation of perfluoroalkylated fluorenes 4 General procedure: The suspension of indenones 1 (1.0mmol), malononitrile2 (1.0mmol), HOAc (0.1 equiv.) and NH4OAc (0.2 equiv.) was stirred in refluxing toluene (5mL) for 12h. When the resultant mixture was cooled to room temperature, methyl perfluoroalk-2-ynoates 3 (1.3 equiv.) and K2CO3 (1.5 equiv.) were added and continued to be stirred at 80°C for another 6h. Then the solvent was removed under reduced pressure and the residue was subjected to column chromatography on silica gel, eluting with petroleum ether/ethyl acetate 20:1 to 10:1 to afford the desired products 4.

Reference： [1]Sun, Zhenhua; Huang, Qi; Han, Jing; He, Weimin; Chen, Jie; Xu, Yuchen; Deng, Hongmei; Shao, Min; Zhang, Hui; Cao, Weiguo [Tetrahedron, 2018, vol. 74, # 16, p. 2073 - 2078]

21
[ 2510-01-2 ]
[ 70577-96-7 ]
methyl 3-amino-4-cyano-1-(heptafluoropropyl)-9H-fluorene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In toluene at 80℃; for 6h;	4.2 General procedure for the preparation of perfluoroalkylated fluorenes 4 General procedure: The suspension of indenones 1 (1.0mmol), malononitrile2 (1.0mmol), HOAc (0.1 equiv.) and NH4OAc (0.2 equiv.) was stirred in refluxing toluene (5mL) for 12h. When the resultant mixture was cooled to room temperature, methyl perfluoroalk-2-ynoates 3 (1.3 equiv.) and K2CO3 (1.5 equiv.) were added and continued to be stirred at 80°C for another 6h. Then the solvent was removed under reduced pressure and the residue was subjected to column chromatography on silica gel, eluting with petroleum ether/ethyl acetate 20:1 to 10:1 to afford the desired products 4.

Reference： [1]Sun, Zhenhua; Huang, Qi; Han, Jing; He, Weimin; Chen, Jie; Xu, Yuchen; Deng, Hongmei; Shao, Min; Zhang, Hui; Cao, Weiguo [Tetrahedron, 2018, vol. 74, # 16, p. 2073 - 2078]

22
[ 2510-01-2 ]
[ 228412-76-8 ]
6-amino-11-p-toluenesulfonyl-11,12-dihydroindeno[2,1-a]carbazole-5-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With cetyltrimethylammonim bromide; caesium carbonate In water at 20℃; for 24h;	4.2. General procedure for the synthesis of compounds 3, 5, 7, 9 General procedure: To a solution of 1 or 4 or 6 or 8 (0.12 mmol) and 2 (0.10 mmol) in H2O (1 mL) was added Cs2CO3 (32.5 mg, 0.10 mmol) and CTAB(2.0 mg, 5 mol%). The mixture was further stirred at room temperature for the indicated time. Once starting material was consumed (monitored by TLC), the mixture was filtered and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 8:1 to 3:1) to afford the corresponding product.
54%	With triethylamine In acetonitrile at 50℃; for 24h; Inert atmosphere;

Reference： [1]Chen, Yong-Zheng; Quan, Bao-Xue; Yuan, Wei-Cheng; Zhang, Ming-Liang; Zhang, Xiao-Mei; Zhao, Jian-Qiang; Zhuo, Jun-Rui [Tetrahedron, 2020]
[2]Cao, Dongdong; Ying, Anguo; Mo, Hanjie; Chen, Dingben; Chen, Gang; Wang, Zhiming; Yang, Jianguo [Journal of Organic Chemistry, 2018, vol. 83, # 20, p. 12568 - 12574]

23
[ 2510-01-2 ]
methyl hexa-2,3,5-trienoate [ No CAS ]
methyl 1,1-dicyano-1,3a,4,5,5a,6-hexahydropentaleno[6a,1-a]indene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With sodium benzoate; triphenylphosphine In toluene at 110℃; for 1h;

Reference： [1]Feng, Jiaxu; Chen, Yingying; Qin, Wenhui; Huang, You [Organic Letters, 2020, vol. 22, # 2, p. 433 - 437]

24
[ 2510-01-2 ]
ethyl hexa-2,3,5-trienoate [ No CAS ]
ethyl 1,1-dicyano-1,3a,4,5,5a,6-hexahydropentaleno[6a,1-a]indene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium benzoate; triphenylphosphine In toluene at 110℃; for 1h;

Reference： [1]Feng, Jiaxu; Chen, Yingying; Qin, Wenhui; Huang, You [Organic Letters, 2020, vol. 22, # 2, p. 433 - 437]

25
[ 2510-01-2 ]
[ 33094-66-5 ]
6-amino-12H-fluoreno[2,1-b]benzofuran-7-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With cetyltrimethylammonim bromide; caesium carbonate In water at 20℃; for 24h;	4.2. General procedure for the synthesis of compounds 3, 5, 7, 9 General procedure: To a solution of 1 or 4 or 6 or 8 (0.12 mmol) and 2 (0.10 mmol) in H2O (1 mL) was added Cs2CO3 (32.5 mg, 0.10 mmol) and CTAB(2.0 mg, 5 mol%). The mixture was further stirred at room temperature for the indicated time. Once starting material was consumed (monitored by TLC), the mixture was filtered and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 8:1 to 3:1) to afford the corresponding product.

Reference： [1]Chen, Yong-Zheng; Quan, Bao-Xue; Yuan, Wei-Cheng; Zhang, Ming-Liang; Zhang, Xiao-Mei; Zhao, Jian-Qiang; Zhuo, Jun-Rui [Tetrahedron, 2020]

26
[ 2510-01-2 ]
[ 10133-33-2 ]
6-amino-12H-benzo[b]fluoreno[1,2-d]thiophene-7-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With cetyltrimethylammonim bromide; caesium carbonate In water at 20℃; for 24h;	4.2. General procedure for the synthesis of compounds 3, 5, 7, 9 General procedure: To a solution of 1 or 4 or 6 or 8 (0.12 mmol) and 2 (0.10 mmol) in H2O (1 mL) was added Cs2CO3 (32.5 mg, 0.10 mmol) and CTAB(2.0 mg, 5 mol%). The mixture was further stirred at room temperature for the indicated time. Once starting material was consumed (monitored by TLC), the mixture was filtered and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 8:1 to 3:1) to afford the corresponding product.

Reference： [1]Chen, Yong-Zheng; Quan, Bao-Xue; Yuan, Wei-Cheng; Zhang, Ming-Liang; Zhang, Xiao-Mei; Zhao, Jian-Qiang; Zhuo, Jun-Rui [Tetrahedron, 2020]

27
[ 2510-01-2 ]
[ 17402-80-1 ]
6-amino-12H-benzo[b]fluoreno[2,1-d]thiophene-5-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With cetyltrimethylammonim bromide; caesium carbonate In water at 20℃; for 24h;	4.2. General procedure for the synthesis of compounds 3, 5, 7, 9 General procedure: To a solution of 1 or 4 or 6 or 8 (0.12 mmol) and 2 (0.10 mmol) in H2O (1 mL) was added Cs2CO3 (32.5 mg, 0.10 mmol) and CTAB(2.0 mg, 5 mol%). The mixture was further stirred at room temperature for the indicated time. Once starting material was consumed (monitored by TLC), the mixture was filtered and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 8:1 to 3:1) to afford the corresponding product.

Reference： [1]Chen, Yong-Zheng; Quan, Bao-Xue; Yuan, Wei-Cheng; Zhang, Ming-Liang; Zhang, Xiao-Mei; Zhao, Jian-Qiang; Zhuo, Jun-Rui [Tetrahedron, 2020]

28
[ 2510-01-2 ]
[ 642-31-9 ]
[ 109-77-3 ]
3-amino-2,4-dicyano-1-(anthracen-9-yl)-9H-fluorene [ No CAS ]