benzo[d][1,3]dioxole-5-carbonitrile [Piperonylonitrile] by Asch

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Date

N O

117 reactions in 2016-06-21 13h:53m:35s (EST) Reaxys

1. Query O

Search as: As drawn, No mixtures, No charges, No radicals 2. Query

(1. Query) AND NOT itemno in (2)

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117 reactions in 2016-06-21 13h:55m:02s (EST) Reaxys

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N O

Rx-ID: 1749293 View in Reaxys 1/117 Yield 99 %

Conditions & References With sodium azide, triflic acid in acetonitrile, Time= 0.0333333h, T= 20 °C , Schmidt reaction Rokade, Balaji V.; Prabhu, Kandikere Ramaiah; Journal of Organic Chemistry; vol. 77; nb. 12; (2012); p. 5364 5370 View in Reaxys

97 %

With oxygen, copper, ammonium chloride in pyridine, Time= 24h, T= 60 °C Capdevielle, Patrice; Lavigne, Andre; Maumy, Michel; Synthesis; nb. 6; (1989); p. 451 - 452 View in Reaxys

95 %

With sodium hydrogen sulphate, hydroxylamine hydrochloride, silica gel, Time= 0.0166667h, microwave irradiation, Condensation, Dehydration Das, Biswanath; Madhusudhan; Venkataiah; Synlett; nb. 10; (1999); p. 1569 - 1570 View in Reaxys

95 %

With PhNHCO2NH2*TsOH in tetrahydrofuran, Time= 2h, Heating, Condensation, elimination Coskun, Necdet; Arikan, Nevin; Tetrahedron; vol. 55; nb. 40; (1999); p. 11943 - 11948 View in Reaxys

95 %

With hydroxylamine hydrochloride, zinc oxide, Time= 0.0111111h, Microwave irradiation, neat (no solvent) Madhusudana Reddy; Pasha; Chinese Chemical Letters; vol. 21; nb. 9; (2010); p. 1025 - 1028 View in Reaxys

94 %

With hydroxylamine hydrochloride, ammonium acetate, Time= 0.0166667h, microwave irradiation, Condensation, Dehydration Das; Ramesh; Madhusudhan; Synlett; nb. 11; (2000); p. 1599 - 1600 View in Reaxys

92 %

With aluminum oxide, hydroxylamine hydrochloride, di(n-butyl)tin oxide, Time= 0.05h, microwave irradiation Yadav; Subba Reddy; Madan; Journal of Chemical Research - Part S; nb. 5; (2001); p. 190 - 191 View in Reaxys

92 %

With XY-zeolite, hydroxylamine hydrochloride, Time= 0.0166667h, microwave irradiation Srinivas; Reddy, E. Bolla; Das, Biswanath; Synlett; nb. 4; (2002); p. 625 - 627 View in Reaxys

92 %

With hydroxylamine hydrochloride, tetrachlorosilane, Time= 0.0166667h, T= 105 °C , microwave irradiation Srinivas; Mahender; Das, Biswanath; Chemistry Letters; vol. 32; nb. 8; (2003); p. 738 - 739 View in Reaxys

91 %

With potassium hydroxide, ammonium hydrogen carbonate, ((n-Bu)4N)2S2O8, copper(I) formate, nickel(II) formate in acetonitrile, Time= 2h, T= 20 °C , Condensation, Oxidation Chen; Fu; Meng; Cheng; Lu; Synthesis; nb. 11; (2000); p. 1519 - 1520 View in Reaxys

91 %

Description 1 : Benzo[d][l,3]dioxole-5-carbonitrile Description 1 : Benzo[d][l,3]dioxole-5-carbonitrile To a solution of benzo[d][l,3]dioxole-5-carbaldehyde (16 g, 107 mmol), sodium formate (14.50 g, 213 mmol) in Formic Acid (150 mL) was added solid hydroxylamine hydrochloride (22.22 g, 320 mmol). The reaction mixture was stirred at 100°C for 2 hr. The solvent was removed out under reduced pressure. Then H20 (200 mL) was added in, the mixture was extracted with DCM (200 mL*3), the combined organic layer was dried over sodium sulfate and evaporated under reduced pressure to afford benzo[d][l,3]dioxole-5-

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carbonitrile as a yellow solid (15 g, 91percent). NMR (400MHz, CDC13) δ: 7. 21 (d, = 8.0 Hz, 1H), 7.03 (s, 1H), 6.86 (d, = 8.0 Hz, 1H), 6.07 (s, 2H). With formic acid, hydroxylamine hydrochloride, sodium formate, Time= 2h, T= 100 °C Patent; GLAXOSMITHKLINE INTELLECTUAL PROPERTY DEVELOPMENT LIMITED; WANG, Rong; LU, Hongtao; WO2013/107336; (2013); (A1) English View in Reaxys 91 %

1 : Description 1: Benzo[d][1,3]dioxole-5-carbonitrile To a solution of benzo[d][1,3]dioxole-5-carbaldehyde (16 g, 107 mmol), sodium formate (14.50 g, 213 mmol) in Formic Acid (150 mL) was added solid hydroxylamine hydrochloride (22.22 g, 320 mmol). The reaction mixture was stirred at 100° C. for 2 hr. The solvent was removed out under reduced pressure. Then H2O (200 mL) was added in, the mixture was extracted with DCM (200 mL×3), the combined organic layer was dried over sodium sulfate and evaporated under reduced pressure to afford benzo[d][1,3]dioxole-5-carbonitrile as a yellow solid (15 g, 91percent). [0132] 1H NMR (400 MHz, CDCl ) δ: 7. 21 (d, T=8.0 Hz, 1H), 7.03 (s, 1H), 6.86 (d, T=8.0 Hz, 1H), 6.07 (s, 2H). 3 With hydroxylamine hydrochloride, sodium formate in formic acid, Time= 2h, T= 100 °C Patent; Lu, Hongtao; Wang, Rong; US2015/80380; (2015); (A1) English View in Reaxys

90 %

With sodium azide, sodium carbonate in acetonitrile, Time= 1h, T= 0 - 25 °C Elmorsy, Saad S.; El-Ahi, Abdel-Aziz S.; Soliman, Hanan; Amer, Fathy A.; Tetrahedron Letters; vol. 36; nb. 15; (1995); p. 2639 - 2640 View in Reaxys

90 %

With hydroxylamine hydrochloride in various solvent(s), T= 110 - 115 °C Kumar, H. M. Sampath; Reddy, B. V. Subba; Reddy, P. Tirupathi; Yadav, J. S.; Synthesis; nb. 4; (1999); p. 586 587 View in Reaxys

88 %

3.3. General Procedure A for the Synthesis of Aromatic Nitriles General procedure: To a solution of an aromatic aldehyde 1 (0.500 mmol, 1.0 equiv) and TMSN3 (115 mg, 1.00 mmol,2.0 equiv) in a premixed HFIP/ACN mixture (2.0 mL, 1:1) in a nitrogen-flushed two dram vial wasadded triflic acid (TfOH; 17.7 L, 0.200 mmol, 0.40 equiv) (exotherm and brisk effervescence due tonitrogen gas evolution was immediately observed). The vial was capped and the reaction mixture wasallowed to stir at rt for 20–75 min. The reaction mixture was concentrated under nitrogen. The residueobtained was suspended in CH2Cl2/hexanes mixture and loaded on a silica gel in a 5 g samplecartridge. Purification using a normal phase silica flash column on a CombiFlash purification systemafforded a corresponding aromatic nitrile 2 upon concentration of appropriate fractions. With triflic acid, trimethylsilylazide in acetonitrile, Time= 1h, T= 20 °C , Sealed tube, Inert atmosphere, Schmidt Reaction Motiwala, Hashim F.; Yin, Qin; Aub, Jeffrey; Molecules; vol. 21; nb. 1; (2016); Art.No: 45 View in Reaxys

87 %

With aluminum oxide, Oxonereg;, hydroxylamine hydrochloride in solid, Time= 0.141667h, microwave irradiation Bose, D. Subhas; Narsaiah, A. Venkat; Tetrahedron Letters; vol. 39; nb. 36; (1998); p. 6533 - 6534 View in Reaxys

87 %

With carbon tetrabromide, hydroxylamine hydrochloride, triethylamine, [BMIM][tppm] in acetonitrile, T= 20 °C Huo, Congde; Wang, Cheng; Hu, Dongcheng; Jia, Xiaodong; Letters in Organic Chemistry; vol. 10; nb. 6; (2013); p. 442 - 444 View in Reaxys

71 %

With Nitroethane, sodium acetate in acetic acid, Time= 4h, Heating Karmarkar, Sanjay N.; Kelkar, Shriniwas L.; Wadia, Murzban S.; Synthesis; nb. 5; (1985); p. 510 - 512 View in Reaxys

65 %

With tert -butyl hydrogen peroxide, Cu(NO3)2 *3H2O, acetic acid, DMFA, Time= 48h, T= 130 °C

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Zhang, Lianpeng; Lu, Ping; Wang, Yanguang; Organic and Biomolecular Chemistry; vol. 14; nb. 5; (2016); p. 1840 - 1840 View in Reaxys 38 %

With ammonium hydroxide, hydrogen peroxide, copper dichloride in isopropyl alcohol, T= 17 - 30 °C , oxidative dehydrogenation Erman; Snow; Williams; Tetrahedron Letters; vol. 41; nb. 35; (2000); p. 6749 - 6752 View in Reaxys

59 % Chromat.

With sulfur, ammonia, sodium nitrite, Time= 4h, T= 100 °C Sato, Ryu; Ityoh, Kaoru; Itoh, Kazumi; Nishina, Hironori; Goto, Takehiko; Saito, Minoru; Chemistry Letters; (1984); p. 1913 - 1916 View in Reaxys

92 % Chromat.

With formic acid, hydroxylamine hydrochloride, silica gel, Time= 0.0166667h, Irradiation Feng, Jun-Cai; Liu, Bin; Dai, Li; Bian, Ning-Sheng; Synthetic Communications; vol. 28; nb. 20; (1998); p. 3765 3768 View in Reaxys Reaction Steps: 2 1: ammonia (g) / CuCl2 / propan-2-ol / 2.5 h / 17 - 30 °C 2: aq. H2O2 / 4 h With ammonia, hydrogen peroxide, copper dichloride in isopropyl alcohol, 1: Condensation / 2: oxidative dehydrogenation Erman; Snow; Williams; Tetrahedron Letters; vol. 41; nb. 35; (2000); p. 6749 - 6752 View in Reaxys Reaction Steps: 2 1: alcohol; water; hydroxylamine 2: acetic acid anhydride With ethanol, water, hydroxylamine, acetic anhydride Marcus; Chemische Berichte; vol. 24; (1891); p. 3652 View in Reaxys Reaction Steps: 2 1: hydroxylamine hydrochloride; sodium hydrogencarbonate / water 2: acetic anhydride / Reflux With hydroxylamine hydrochloride, acetic anhydride, sodium hydrogencarbonate in water Wani, Mohmmad Younus; Bhat, Abdul Roouf; Azam, Amir; Choi, Inho; Athar, Fareeda; European Journal of Medicinal Chemistry; vol. 48; (2012); p. 313 - 320 View in Reaxys Reaction Steps: 2 1: sodium tetrahydroborate 2: CuII(ClO4)2*6H2O; trimethylsilylazide; 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / 1,2-DICHLOROETHANE / 6 h / 60 °C With sodium tetrahydroborate, CuII(ClO4)2*6H2O, trimethylsilylazide, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in 1,2-DICHLOROETHANE Rokade, Balaji V.; Malekar, Sanjeev K.; Prabhu, Kandikere Ramaiah; Chemical Communications; vol. 48; nb. 44; (2012); p. 5506 - 5508 View in Reaxys Reaction Steps: 2 1: hydroxylamine hydrochloride; sodium hydrogencarbonate / water 2: acetic anhydride / 24 h / |Reflux With hydroxylamine hydrochloride, acetic anhydride, sodium hydrogencarbonate in water

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Arshad, Mohammad; Bhat, Abdul Roouf; Pokharel, Smritee; Kim, Ji-Eun; Lee, Eun Ju; Athar, Fareeda; Choi, Inho; European Journal of Medicinal Chemistry; vol. 71; (2014); p. 229 - 236 View in Reaxys 95 %Spectr.

With borate(1-), tetrafluoro-,hydrogen (1:1) ethane, 1,1'-oxybis-, sodium azide, acetic acid, Time= 1h, T= 20 °C , Schmidt Reaction, Reagent/catalyst, Solvent, Time Hazarika, Nabajyoti; Baishya, Gakul; European Journal of Organic Chemistry; vol. 2014; nb. 26; (2014); p. 5686 5690,5 View in Reaxys Reaction Steps: 2 1: pyridine / dichloromethane / 0.08 h / 20 °C 2: [Pip*(O)][BF4] / dichloromethane / 12 h / 20 °C With pyridine, [Pip*(O)][BF4] in dichloromethane Kelly, Christopher B.; Lambert, Kyle M.; Mercadante, Michael A.; Ovian, John M.; Bailey, William F.; Leadbeater, Nicholas E.; Angewandte Chemie - International Edition; vol. 54; nb. 14; (2015); p. 4241 - 4245 View in Reaxys With tert -butyl hydrogen peroxide, Cu(NO3)2 *3H2O, acetic acid, DMFA, Time= 48h, T= 130 °C Zhang, Lianpeng; Lu, Ping; Wang, Yanguang; Organic and Biomolecular Chemistry; vol. 13; nb. 30; (2015); p. 8322 - 8329 View in Reaxys N-(Diphenylmethyl)amides 3 and N-(1-Adamantyl)amides 7 via the Schmidt and Ritter Reaction Sequence; General Procedure General procedure: To a solution of an aldehyde (1 mmol, 1 equiv) and NaN3 (1.5 mmol,1.5 equiv) in AcOH (2 mL) was added HBF4·OEt2 (2–3 mmol, 2–3equiv), and the reaction mixture was stirred for 1 h. To this reactionmixture was added benzhydrol (2) or 1-adamantanol (6; 1.0 mmol,1.0 equiv) and HBF4·OEt2 (2–3 mmol, 2–3 equiv). Then, the reactionmixture was allowed to stir for an additional 2–4 h. After completionof the reaction (TLC), sat. aq NaHCO3 solution (20 mL) was added tothe mixture. The solid product which precipitated from the reactionmixture was filtered and washed thoroughly with distilled water (50mL). The solid was dried under reduced pressure to give the productwhich was further purified by recrystallization from ethanol [N-(diphenylmethyl)amides] or hexane [N-(1-adamantyl)amides]. With borate(1-), tetrafluoro-,hydrogen (1:1) ethane, 1,1'-oxybis-, sodium azide, acetic acid, Time= 1h, T= 20 °C , Schmidt Reaction Hazarika, Nabajyoti; Baishya, Gakul; Phukan, Prodeep; Synthesis (Germany); vol. 47; nb. 18; (2015); p. 2851 2859; Art.No: SS-2015-Z0137-OP View in Reaxys With 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy, ammonium acetate, oxygen, nitric acid, acetic acid, sodium nitrite, Time= 12h, T= 50 °C Noh, Ji-Hyun; Kim, Jinho; Journal of Organic Chemistry; vol. 80; nb. 22; (2015); p. 11624 - 11628 View in Reaxys N

Rx-ID: 9124644 View in Reaxys 2/117 Yield 100 %

Conditions & References With 2,3'-bipyridine, ammonium hydroxide, copper(l) iodide, 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical, oxygen in ethanol, Time= 24h, T= 20 °C Yin, Weiyu; Wang, Chengming; Huang, Yong; Organic Letters; vol. 15; nb. 8; (2013); p. 1850 - 1853 View in Reaxys

99 %

Stage 1: With 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical, 1,3-Diiodo-5,5-dimethyl-2,4-imidazolidinedione in dichloromethane, Time= 0.5h, T= 20 °C , Inert atmosphere

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Stage 2: With ammonia, iodine in dichloromethane, water, Time= 2h, T= 20 °C , Inert atmosphere Shimojo, Hiroyuki; Moriyama, Katsuhiko; Togo, Hideo; Synthesis (Germany); vol. 45; nb. 15; (2013); p. 2155 2164; Art.No: SS-2013-F0311-OP View in Reaxys 95 %

With ammonium hydroxide, 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical, [{(MeOH)Cu(OAc)}(μ-k2:k1-2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid(-H))]2*0.5H2O, tetraethylammonium iodide, oxygen, potassium carbonate in water, Time= 24h, T= 60 °C , p= 760.051Torr Xie, Jing-Bo; Bao, Jia-Jing; Li, Hong-Xi; Tan, Da-Wei; Li, Hai-Yan; Lang, Jian-Ping; RSC Advances; vol. 4; nb. 96; (2014); p. 54007 - 54017 View in Reaxys

93 %

Oxidative Conversion of Alcohols into Nitriles; GeneralProcedure: General procedure: To a solution of alcohol (1 mmol) in MeCN–H2O (9:1, 3 mL) were successively added TEMPO (7.8 mg,5 molpercent), NH4OAc (0.308 g, 4 equiv), and PhI(OAc)2 (0.708g, 2.2 equiv). The suspension was stirred at roomtemperature (progress of the reaction was monitored byTLC) for the reaction time indicated in Table 2. The resultantclear two-phase reaction mixture was concentrated, dilutedwith H2O and Et2O, and the organic layer was dried (Na2SO4), filtered, and evaporated under reduced pressure.The residue was purified by flash column chromatography(PE–Et2O or PE–CH2Cl2) to give 2. With 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical, [bis(acetoxy)iodo]benzene, ammonium acetate in water, acetonitrile, Time= 10h, T= 20 °C Vatele, Jean-Michel; Synlett; vol. 25; nb. 9; (2014); p. 1275 - 1278; Art.No: ST-2014-D0186-L View in Reaxys

90 %

With potassium hydroxide, ammonium hydrogen carbonate, ((n-Bu)4N)2S2O8, coppper(II) formate, nickel(II) formate in isopropyl alcohol, Time= 1.5h, T= 25 °C Chen, Fen-Er; Li, Yong-Ye; Xu, Mei; Jia, Hui-Qing; Synthesis; nb. 13; (2002); p. 1804 - 1806 View in Reaxys

82 %

With copper(II)(perchlorate)2*6H2O, trimethylsilylazide, 2,3-dicyano-5,6-dichloro-p-benzoquinone in 1,2-dichloroethane, Time= 6h, T= 60 °C Rokade, Balaji V.; Malekar, Sanjeev K.; Prabhu, Kandikere Ramaiah; Chemical Communications; vol. 48; nb. 44; (2012); p. 5506 - 5508 View in Reaxys

70 %

With CuCl2·2H2O, ammonium formate, potassium carbonate in neat (no solvent), Time= 24h, T= 135 °C , p= 760.051Torr , Sealed tube, Schlenk technique, Green chemistry Yadav, Dilip Kumar T.; Bhanage, Bhalchandra M.; European Journal of Organic Chemistry; nb. 23; (2013); p. 5106 - 5110 View in Reaxys

N N

Rx-ID: 10068935 View in Reaxys 3/117 Yield 92%

Conditions & References 4.1.2 General procedure for the synthesis of piperonyl nitrile [B] A mixture of piperonal oxime A (30mmol) and acetic anhydride (20mL) was refluxed for 24h; vigorous stirring is essential. The reaction was monitored by thin layer chromatography. After completion, the reaction mixture was poured into ice cold water to obtain a solid precipitate. The precipitate was filtered, and air dried. Yield 92percent; mp 95– 98°C; white crystals; IR νmax (cm−1): 2928 (CH–Ar), 2204 (CN); 1H NMR DMSO/(ppm): 7.18–6.90 (m, 3H, Ar–H), 6.03 (s, 2H, –O–CH2–O–). With acetic anhydride, Time= 24h, Reflux

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Typical procedure C to preparebenzonitriles from benzaldoximes with CBrCl3 and 2 equiv. PPh3 General procedure: BrCCl3 (650 mg, 3.3 mmol) was added to PPh3 (870 mg, 3.3 mmol) in dry CH2Cl2 (10 mL). The resulting mixture was stirred at room temperature for 20 min, during which time the solution turned from yellow to red–brownish in colour. Thereafter, 4‑ethoxybenzaldoxime (4n, 500 mg, 3.05 mmol) was added. The reaction mixture was heated under reflux for 25 min. Then, triphenylphosphine (870 mg, 3.3 mmol) was added,and the mixture was stirred for 8 h at reflux. The cooled reaction mixture was concentrated under reduced pressure and subjected directly to column chromatography on silica gel (CH2Cl2–hexane 5 : 1) to give 2v as a colourless solid. With bromotrichloromethane, triphenylphosphine in dichloromethane, Time= 8h, Reflux Jasem, Yosef Al; Barkhad, Mohamed; Khazali, Mona Al; Butt, Hifsa Pervez; El-Khwass, Noha Ashraf; Azani, Mariam Al; Hindawi, Bassam Al; Thiemann, Thies; Journal of Chemical Research; vol. 38; nb. 2; (2014); p. 80 84 View in Reaxys

90 %

With iodine, triphenylphosphine in dichloromethane, Time= 3.5h, T= 20 °C Venkat Narsaiah; Sreenu; Nagaiah; Synthetic Communications; vol. 36; nb. 2; (2006); p. 137 - 140 View in Reaxys

90 %

With Xanthobin, DBU in DMFA, Time= 0.0277778h, Microwave irradiation, chemoselective reaction Soltani Rad, Mohammad Navid; Behrouz, Somayeh; Nekoei, Abdo-Reza; Synlett; vol. 23; nb. 8; (2012); p. 1191 - 1198 View in Reaxys

86 %

With Sn1.9WClO6.3*9H2O in o-xylene, Time= 1h, T= 149 °C , p= 760.051Torr Yamaguchi, Kazuya; Fujiwara, Hiroshi; Ogasawara, Yoshiyuki; Kotani, Miyuki; Mizuno, Noritaka; Angewandte Chemie - International Edition; vol. 46; nb. 21; (2007); p. 3922 - 3925 View in Reaxys Reaction Steps: 2 1.1: POCl3; DMF / 1 h / 0 - 5 °C 1.2: 92 percent / NaOH / H2O / 0.02 h / Heating 2.1: 85 percent / POCl3; DMF / 2 h / 0 - 5 °C With DMFA, phosphoryl chloride Kusurkar, Radhika; Goswami, Shailesh; Vyas, Sandhya; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 42; nb. 12; (2003); p. 3148 - 3151 View in Reaxys With 1-Methylpyrrolidine, Time= 4h, T= 115 °C van Veldhoven, Jacobus P.D.; Chang, Lisa C.W.; von Frijtag Drabbe Kuenzel, Jacobien K.; Mulder-Krieger, Thea; Struensee-Link, Regina; Beukers, Margot W.; Brussee, Johannes; IJzerman, Adriaan P.; Bioorganic and Medicinal Chemistry; vol. 16; nb. 6; (2008); p. 2741 - 2752 View in Reaxys 1.2 : 2) General Procedure for the Synthesis of Piperonal Nitrile [b] General procedure: 2) General Procedure for the Synthesis of Piperonal Nitrile [b]:_To a 250 ml round-bottomed flask, a mixture of piperonal oxime and acetic anhydride (20 mL) was added and refluxed with stirring for 24 h. The reaction mixture was poured into ice cold water to obtain a solid precipitate. The precipitate was filtered, and air dried. With acetic anhydride, Time= 24h, Reflux Patent; INDUSTRY-ACADEMIC COOPERATION FOUNDATION, YEUNGNAM UNIVERSITY; Choi, In Ho; Fareeda, Athar; Abdul, Roouf Bhat; US2015/291566; (2015); (A1) English View in Reaxys

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N H 2N

Rx-ID: 1772033 View in Reaxys 4/117 Yield 99 %

Conditions & References With copper(I) chloride, 4 A molecular sieve, oxygen in pyridine, Time= 24h, T= 60 °C Capdevielle, Patrice; Lavigne, Andre; Maumy, Michel; Synthesis; nb. 6; (1989); p. 453 - 454 View in Reaxys

97 %

With dmap, copper(l) iodide, ABNO, oxygen, dtbbpy in acetonitrile, Time= 15h, T= 20 °C , p= 760.051Torr , Reagent/catalyst Kim, Jinho; Stahl, Shannon S.; ACS Catalysis; vol. 3; nb. 7; (2013); p. 1652 - 1656 View in Reaxys

93 %

With ammonium hydroxide, oxygen in tert-Amyl alcohol, Time= 15h, T= 110 °C , p= 1500.15Torr , Autoclave, Green chemistry Natte, Kishore; Jagadeesh, Rajenahally V.; Sharif, Muhammad; Neumann, Helfried; Beller, Matthias; Organic and Biomolecular Chemistry; vol. 14; nb. 13; (2016); p. 3356 - 3359 View in Reaxys

90 %

With 2,2,6,6-tetramethyl-piperidine-N-oxyl, free radical, trichloroisocyanuric acid in dichloromethane, Time= 2h, T= 10 °C Chen, Fen-Er; Kuang, Yun-Yan; Dai, Hui-Fang; Lu, Liang; Huo, Ming; Synthesis; nb. 17; (2003); p. 2629 - 2631 View in Reaxys

85 %

With 2,6-dimethylpyridine, 2,2,6,6-tetramethyl-piperidine-N-oxyl, lithium perchlorate in acetonitrile, T= 23 °C , electrolysis, a platinum gauze electrode, +0.33 V (vs. Ag/Ag(1+)) Semmelhack, M. F.; Schmid, Christopher R.; Journal of the American Chemical Society; vol. 105; nb. 22; (1983); p. 6732 - 6734 View in Reaxys

81 %

With sodium bromide in methanol, T= 10 °C , electrooxidation (0.3 A, 75 mA/cm2, 5-7 V) 6.4 F/mol Shono, Tatsuya; Matsumura, Yoshihiro; Inoue, Kenji; Journal of the American Chemical Society; vol. 106; nb. 20; (1984); p. 6075 - 6076 View in Reaxys

81 %

With pyridine, Oxonereg;, 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy, Pyridine hydrobromide in dichloromethane, Time= 12h, T= 20 °C , Green chemistry Lambert, Kyle M.; Bobbitt, James M.; Eldirany, Sherif A.; Kissane, Liam E.; Sheridan, Rose K.; Stempel, Zachary D.; Sternberg, Francis H.; Bailey, William F.; Chemistry - A European Journal; vol. 22; nb. 15; (2016); p. 5156 - 5159 View in Reaxys

77 %

With tetrabutylammomium bromide, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in acetonitrile, Time= 0.0833333h, T= 20 °C , Inert atmosphere, Molecular sieve Drouet, Fleur; Fontaine, Patrice; Masson, Geraldine; Zhu, Jieping; Synthesis; nb. 8; (2009); p. 1370 - 1374; Art.No: T19708SS View in Reaxys With pyridine, copper(l) iodide, oxygen, Time= 24h, T= 60 °C , mol. sieves, Yield given Capdevielle; Lavigne; Sparfel; Baranne-Lafont; Cuong; Maumy; Tetrahedron Letters; vol. 31; nb. 23; (1990); p. 3305 - 3308 View in Reaxys

96 %Chromat.

With ammonium hydroxide, oxygen in tert-Amyl alcohol, Time= 15h, T= 110 °C , p= 2250.23Torr , Autoclave, Green chemistry

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Jagadeesh, Rajenahally V.; Junge, Henrik; Beller, Matthias; ChemSusChem; vol. 8; nb. 1; (2015); p. 92 - 96 View in Reaxys O

N H

Rx-ID: 40134423 View in Reaxys 5/117 Yield

Conditions & References

89 %

4.2.26. Piperonylonitrile (2-29) General procedure: To an ice bath-cooled solution of a secondary amide (1.0 mmol) and 2-fluoropyridine (1.2 mmol) in anhydrous CH2Cl2 (5 mL) was added Tf2O (1.1 mmol). After being stirred for 0.5 h, the reaction mixture was warmed to 30 °C and stirred until completion of the reaction (monitored by TLC analysis). The reaction was quenched with 1 m HCl (1.0 mL), and the mixture was extracted with CH2Cl2 (3×10 mL). The combined organic layers were washed with saturated sodium carbonate (5 mL) and brine (5 mL), dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel eluting with ethyl acetate/petroleum ether to afford the corresponding nitrile. With 2-fluoro-pyridine, trifluoromethylsulfonic anhydride in dichloromethane, Time= 3h, T= 0 - 30 °C , chemoselective reaction Geng, Hui; Huang, Pei-Qiang; Tetrahedron; vol. 71; nb. 23; (2015); p. 3795 - 3801 View in Reaxys

O S Cl

N N

Rx-ID: 23226875 View in Reaxys 6/117 Yield

Conditions & References

99 %

2.2 : Step 2) Step 2) The compound prepared in Step 1(15.7g, 0.095mol) was dissolved in methylene chloride(160mlitre), triethylamine(32.9mlitre, 0.236mol) was added thereto, and the resulting mixture was cooled down to 0°C. Methane-sulfonylchloride(8.82mlitre, 0.114mol) was added to the reaction solution, which was then stirred for 30 minutes at the same temperature. The reaction mixture was filtered and then the filtrate was sequentially washed with 1N-hydrochloric acid solution, saturated sodium bicarbonate solution and saturated saline solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated to give benzo[3,4-d]1,3-dioxolan-5-carbonitrile(13.83g, Yield 99percent) as a pale yellow solid. 1H NMR(300MHz, CDCl ): δ 6.09(s, 2H), 6.88(d, 1H, J = 8.1 Hz), 7.05(d, 1H, J = 1.5 Hz), 7.23(dd, 1H, J = 1.5, 8.1 3 Hz) 13C NMR(75MHz, CDCl ): δ 151.9, 148.4, 128.6, 119.2, 111.8, 109.5, 105.4, 102.6 3 With triethylamine in dichloromethane, Time= 0.5h, T= 0 °C Patent; Choongwae Pharma Co., Ltd.; EP1073428; (2004); (B1) English View in Reaxys

N N (v6)

Fe 4N

N3 H N

O S

N 4

N O

K+

Rx-ID: 30111251 View in Reaxys 7/117 Yield 96 %

Conditions & References With CM-phos, palladium diacetate, potassium carbonate in water, Time= 18h, T= 80 °C , Inert atmosphere

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Yeung, Pui Yee; So, Chau Ming; Lau, Chak Po; Kwong, Fuk Yee; Angewandte Chemie - International Edition; vol. 49; nb. 47; (2010); p. 8918 - 8922 View in Reaxys 71 %

general procedures for the cyanation of aryl chlorides and mesylates General procedure: An oven-dried Schlenk tube was evacuated and backfilled with nitrogen. The Schlenk tube was charged with Pd(OAc)2 (4.5 mg, 0.02 mmol ), L1 (36.5 mg, 0.08 mmol), PhB(OH)2 (6.1 mg, 0.05 mmol), and t-BuOH (2 mL), and the mixture was stirred for half hour at 50 °C. After cooling to r.t., aryl chloride or mesylates (1.00 mmol), K4[Fe(CN)6]·3H2O (211.2 mg, 0.50 mmol), K2CO3 (138.2 mg, 1.00 mmol), and H2O (2 mL) were added. The septum was replaced with an inside reflux condenser, and then the Schlenk tube was placed in an oil bath preheated to 100 °C (120 °C for aryl mesylates) with stirring for 6 h (24 h for aryl mesylates). Then the reaction mixture was allowed to cool to r.t., extracted with CH2Cl2, and concentrated under reduced pressure. The crude material was purified by column chromatography on silica gel. With di-tert-butyl{2′-isopropoxy-[1,1′-binaphthalen]-2-yl}phosphane, palladium diacetate, potassium carbonate, 3,4,5trimethoxyphenylboronic acid in water, tert-butyl alcohol, Time= 24h, T= 120 °C , Inert atmosphere, Schlenk technique, Suzuki-Miyaura Coupling Tu, Yahui; Zhang, Yi; Xu, Sheng; Zhang, Zhaoguo; Xie, Xiaomin; Synlett; vol. 25; nb. 20; (2014); p. 2938 - 2942; Art.No: ST-2014-W0578-L View in Reaxys N N

N (v6)

Fe 4N

N3 H

N 4

K+

Rx-ID: 30335123 View in Reaxys 8/117 Yield

Conditions & References

90 %

With CM-phos, palladium diacetate, sodium carbonate, triethylamine in water, acetonitrile, Time= 18h, T= 70 °C Yeung, Pui Yee; So, Chau Ming; Lau, Chak Po; Kwong, Fuk Yee; Organic Letters; vol. 13; nb. 4; (2011); p. 648 651 View in Reaxys

71 %

general procedures for the cyanation of aryl chlorides and mesylates General procedure: An oven-dried Schlenk tube was evacuated and backfilled with nitrogen. The Schlenk tube was charged with Pd(OAc)2 (4.5 mg, 0.02 mmol ), L1 (36.5 mg, 0.08 mmol), PhB(OH)2 (6.1 mg, 0.05 mmol), and t-BuOH (2 mL), and the mixture was stirred for half hour at 50 °C. After cooling to r.t., aryl chloride or mesylates (1.00 mmol), K4[Fe(CN)6]·3H2O (211.2 mg, 0.50 mmol), K2CO3 (138.2 mg, 1.00 mmol), and H2O (2 mL) were added. The septum was replaced with an inside reflux condenser, and then the Schlenk tube was placed in an oil bath preheated to 100 °C (120 °C for aryl mesylates) with stirring for 6 h (24 h for aryl mesylates). Then the reaction mixture was allowed to cool to r.t., extracted with CH2Cl2, and concentrated under reduced pressure. The crude material was purified by column chromatography on silica gel. With di-tert-butyl{2′-isopropoxy-[1,1′-binaphthalen]-2-yl}phosphane, palladium diacetate, potassium carbonate, 3,4,5trimethoxyphenylboronic acid in water, tert-butyl alcohol, Time= 6h, T= 100 °C , Inert atmosphere, Schlenk technique, Suzuki-Miyaura Coupling Tu, Yahui; Zhang, Yi; Xu, Sheng; Zhang, Zhaoguo; Xie, Xiaomin; Synlett; vol. 25; nb. 20; (2014); p. 2938 - 2942; Art.No: ST-2014-W0578-L View in Reaxys O O

N O

Rx-ID: 31794202 View in Reaxys 9/117 Yield 74 %

Conditions & References 4.2. Typical procedure for conversion of aromatic ethyl esters into aromatic nitriles

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General procedure: NaOtBu (98percent purity, 353 mg, 3.6 mmol) was dried by a vacuum pump for 30 min at room temperature. To a solution of NaOtBu in THF (3 mL) was added DIBAL-H (1.04 M, 3.27 mL, 3.4 mmol) at 0 °C under argon atmosphere and the obtained mixture was stirred for 1 h at room temperature. Then, ethyl benzoate (150.06 mg, 2.0 mmol) in THF (4 mL) was added to the solution at 0 °C, and the obtained mixture was stirred for 4 h. Finally, aq NH3 (concentration: 28.0percent-30.0percent, 4 mL) and I2 (2.08 g, 4.1 equiv) were added at 0 °C, and the obtained mixture was stirred for 3 h at room temperature. Then the reaction mixture was poured into saturated aq Na2SO3 solution (10 mL) and extracted with ethyl acetate (15 mL.x.3). The organic layer was dried over Na2SO4 and filtered. After removal of the solvent under reduced pressure, the residue was treated with flash short column chromatography on silica gel (eluent: hexane/ethyl acetate=9:1) to afford benzonitrile (156.7 mg, 76percent yield) Stage 1: With sodium diisobutyl-tert-butoxyaluminium hydride in tetrahydrofuran, Time= 4h, T= 0 °C , Inert atmosphere Stage 2: With ammonia, iodine in tetrahydrofuran, water, Time= 3h, T= 0 - 20 °C Suzuki, Yusuke; Moriyama, Katsuhiko; Togo, Hideo; Tetrahedron; vol. 67; nb. 41; (2011); p. 7956 - 7962 View in Reaxys N

Rx-ID: 34648071 View in Reaxys 10/117 Yield

Conditions & References

62 %

3.2 : Typical experimental procedure for conversion of aromaticbromides into aromatic nitriles with Mg, DMF, I2, and aqNH3 General procedure: To a flask containing Mg turnings (0.29 g, 12 mmol) was added1-bromo-4-methylbenzene (1.37 g, 8.0 mmol) in THF (8 mL) at room temperature. After being stirred for 2 h, DMF (1.3 mL,12 mmol) was added to the reaction mixture. The obtained mixturewas stirred for 2 h at 0 ° C. Then, aq NH3 (7 mL, 28-30percent) and I2 (4.06 g, 16 mmol) were added to the reaction mixture. After beingstirred for 2 h at room temperature, the reaction mixture waspoured into satd aq Na2SO3 solution and was extracted with CHCl3 (3*30 mL). The organic layer was dried over Na2SO4 and filtered.After removal of the solvent, the residue was purified by shortcolumn chromatography on silica gel (eluent: hexane/ethylacetate=9:1, v/v) to provide pure 4-methyl-1-benzonitrile (0.77 g) in 82percent yield. Stage 1: With magnesium in tetrahydrofuran, Time= 2h, T= 20 °C Stage 2: With N,N-dimethyl-formamide in tetrahydrofuran, Time= 2h, T= 0 °C Stage 3: With ammonia, iodine in tetrahydrofuran, water, Time= 2h, T= 20 °C Ishii, Genki; Harigae, Ryo; Moriyama, Katsuhiko; Togo, Hideo; Tetrahedron; vol. 69; nb. 5; (2013); p. 1462 1469 View in Reaxys H

N O O

O O

Rx-ID: 5081132 View in Reaxys 11/117 Yield 99 %

Conditions & References With rhenic(VII) acid in water, 1,3,5-trimethyl-benzene, Time= 1h, Heating Ishihara, Kazuaki; Furuya, Yoshiro; Yamamoto, Hisashi; Angewandte Chemie - International Edition; vol. 41; nb. 16; (2002); p. 2983 - 2986 View in Reaxys

99 %

With rhenic(VII) acid in water, 1,3,5-trimethyl-benzene, Time= 1h, Heating Furuya, Yoshiro; Ishihara, Kazuaki; Yamamoto, Hisashi; Bulletin of the Chemical Society of Japan; vol. 80; nb. 2; (2007); p. 400 - 406 View in Reaxys

92 %

4.1. Synthesis of 5-(1,3-benzodioxol-5-yl)-1H-tetrazole (3a) 5-(1,3-benzodioxol-5-yl)-1H-tetrazole was synthesized from 1,3-benzodioxole-5-carbonitrile by following a reported procedure [46]. The requisite nitrile (2) was prepared from Piperonal (1,3-benzodioxole-5-carbaldehyde) via oxime

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formation, followed by dehydration with acetic anhydride, following a reported procedure [45]. Nitrile (2.95 g, 20 mmol), sodium azide (1.43 g, 22 mmol) and zinc bromide (4.50 g, 20 mmol), were put in 60 mL of water. 5 mL of isopropanol was also added to stop the formation of clumps. The reaction mixture was refluxed for 24 h and monitored by TLC; vigorous stirring is essential. After 24 h HCl (3 N, 30 mL) and ethyl acetate (100 mL) were added, and vigorous stirring was continued until no solid was present and the aqueous layer had a pH of 1. If necessary, additional ethyl acetate was added. The organic layer was isolated and the aqueous layer extracted with 2 .x. 100 mL of ethyl acetate. The combined organic layers were evaporated, 200 mL of 0.25 N NaOH was added, and the mixture was stirred for 30 min, until the original precipitate was dissolved and a suspension of zinc hydroxide was formed. The suspension was filtered, and the solid washed with 20 mL of 1 N NaOH. To the filtrate was added 50 mL of 3 N HCl with vigorous stirring causing the tetrazole to precipitate. The tetrazole was filtered and washed with 2 .x. 50 mL of 3 N HCl and dried in a drying oven to furnish the tetrazole as a white powder. With acetic anhydride, Reflux Wani, Mohmmad Younus; Bhat, Abdul Roouf; Azam, Amir; Choi, Inho; Athar, Fareeda; European Journal of Medicinal Chemistry; vol. 48; (2012); p. 313 - 320 View in Reaxys 73 %

Time= 0.075h, Irradiation, Dehydration Sabitha, Gowravaram; Syamala; Synthetic Communications; vol. 28; nb. 24; (1998); p. 4577 - 4580 View in Reaxys

O O

N O

O P

N H

O O O

Rx-ID: 1821699 View in Reaxys 12/117 Yield

Conditions & References

28 %, 51 %

With tris-(2-chloro-ethyl)-amine, sulfuric acid in chloroform, Time= 0.0833333h, T= 0 °C Sprecher, Milon; Kost, Daniel; Journal of the American Chemical Society; vol. 116; nb. 3; (1994); p. 1016 - 1026 View in Reaxys

51 %, 28 %

Br –

C 2N

Zn 2+

Rx-ID: 39621343 View in Reaxys 13/117 Yield

Conditions & References

99 %

With t-BuXPhos palladium(II) biphenyl-2-amine mesylate in tetrahydrofuran, water, Time= 18h, T= 40 °C , Inert atmosphere Cohen, Daniel T.; Buchwald, Stephen L.; Organic Letters; vol. 17; nb. 2; (2015); p. 202 - 205 View in Reaxys

I N

C–

Na +

Rx-ID: 35916899 View in Reaxys 14/117 Yield

Conditions & References Synthesis of 5-substituted-1H-tetrazoles (general procedure) General procedure: Synthesis of 5-substituted-1H-tetrazoles (general procedure): To a solution of aryliodide (1 mmol) in DMF (5 ml) was added sodium cyanide (1.2 mmol), catalyst(10 mol percent) and the reaction mixture was

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stirred under heating at 100° C for appropriate time to obtain nitrile compound (see Table 1). To the nitrile compound generated in situ was added sodium azide (1.5 mmol) and the reaction was continued till the complete conversion of nitrile to tetrazole. After the completion of the reaction, the catalyst from the reaction mixture was easily separated out by centrifuging the reaction mixture. After the separation of the catalyst the crude material was then taken into ethyl acetate and washed with 5 N HCl and the layers separated. The organic layer was then washed with water, dried over anhyd sodium sulfate and concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography using appropriate solvent mixtures to obtain the pure products (see Tables 1and 2). Detailed experimental conditions and spectroscopic data were given insupplementary data. With copper oxide in N,N-dimethyl-formamide, T= 100 °C Yapuri, Umanadh; Palle, Sadanandam; Gudaparthi, Omprakash; Narahari, Srinivasa Reddy; Rawat, Dhwajbahadur K.; Mukkanti, Khagga; Vantikommu, Jyothi; Tetrahedron Letters; vol. 54; nb. 35; (2013); p. 4732 - 4734 View in Reaxys

N O O

Rx-ID: 2222923 View in Reaxys 15/117 Yield

Conditions & References

99 %

With 4-(N,N-dimethlyamino)pyridine, Sn(thiophenolate)4, tributylphosphine, diethylazodicarboxylate in dichloromethane, Time= 0.0833333h, T= 0 °C Urpi; Vilarrasa; Tetrahedron Letters; vol. 31; nb. 51; (1990); p. 7497 - 7498 View in Reaxys

N N

Rx-ID: 34136411 View in Reaxys 16/117 Yield 82 %

Conditions & References With 1,4-diaza-bicyclo[2.2.2]octane, tert.-butylhydroperoxide, potassium iodide in water, Time= 8h, T= 20 °C Lamani, Manjunath; Devadig, Pradeep; Prabhu, Kandikere Ramaiah; Organic and Biomolecular Chemistry; vol. 10; nb. 14; (2012); p. 2753 - 2759 View in Reaxys

NH 2 O

N O

Rx-ID: 549042 View in Reaxys 17/117 Yield 89 %

Conditions & References With trifluoromethylsulfonic anhydride, triethylamine in dichloromethane, Time= 0.333333h, Ambient temperature Bose, D. Subhas; Jayalakshmi, B.; Synthesis; nb. 1; (1999); p. 64 - 65 View in Reaxys

85 %

With N,N-dimethyl-formamide, trichlorophosphate, Time= 2h, T= 0 - 5 °C Kusurkar, Radhika; Goswami, Shailesh; Vyas, Sandhya; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 42; nb. 12; (2003); p. 3148 - 3151 View in Reaxys With phosphorus pentachloride Andrewes; King; Walker; Proceedings of the Royal Society of London, Series B: Biological Sciences; vol. 133; (1946); p. 20,30 View in Reaxys

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N E

Rx-ID: 9465934 View in Reaxys 18/117 Yield

Conditions & References

85 %

With acetic acid, sodium nitrite in dimethyl sulfoxide, Time= 1.5h, T= 35 °C Ran, Chongzhao; Yang, Genjin; Wu, Taizhi; Xie, Meihua; Tetrahedron Letters; vol. 44; nb. 44; (2003); p. 8061 8062 View in Reaxys

-1 6N 4

Fe 2+

K+

Rx-ID: 28752926 View in Reaxys 19/117 Yield

Conditions & References

58 %

With palladium (II) trifluoroacetate, 2-(di-tert-butylphosphino)-1-(2,6-diisopropylphenyl)-1H-imidazole, sodium carbonate in N,N-dimethyl acetamide, Time= 16h, T= 140 °C , Inert atmosphere Schareina, Thomas; Jackstell, Ralf; Schulz, Thomas; Zapf, Alexander; Cotte, Alain; Gotta, Matthias; Beller, Matthias; Advanced Synthesis and Catalysis; vol. 351; nb. 4; (2009); p. 643 - 648 View in Reaxys N N

N (v6)

Fe 4N

N3 H

N 4

K+

Rx-ID: 32667129 View in Reaxys 20/117 Yield

Conditions & References

88 %

With tetrakis(triphenylphosphine) palladium(0), DBU in water, tert-butanol, Time= 12h, T= 85 °C , Inert atmosphere Zhang, Dengyou; Sun, Haifeng; Zhang, Lei; Zhou, Yu; Li, Chunpu; Jiang, Hualiang; Chen, Kaixian; Liu, Hong; Chemical Communications; vol. 48; nb. 23; (2012); p. 2909 - 2911 View in Reaxys

60 %

With C30H27FeN2OP, palladium diacetate, sodium carbonate in 1,4-dioxane, water, Time= 3h, T= 100 °C , Inert atmosphere, Schlenk technique koch, Karel; Csaov, Ivana; tpnika, Petr; Organometallics; vol. 34; nb. 10; (2015); p. 1942 - 1956 View in Reaxys N O O

O Cl

O O

Rx-ID: 39531637 View in Reaxys 21/117 Yield 78 %

Conditions & References Stage 1: With zinc dibromide in dichloromethane, Time= 20h, T= 20 °C Stage 2: With ammonium hydroxide, iodine in dichloromethane, Time= 6h, T= 20 °C Tamura, Toshiyuki; Moriyama, Katsuhiko; Togo, Hideo; European Journal of Organic Chemistry; vol. 2015; nb. 9; (2015); p. 2023 - 2029 View in Reaxys

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aqueous sodium sulfite

cupric chloride

O O

N O O

Rx-ID: 24426229 View in Reaxys 22/117 Yield

Conditions & References 39 : Synthesis of Piperonylonitrile (3.4-methylenedioxybenzonitrile) from Piperonal (3,4-methylenedioxybenzaldehyde). Example 39 Synthesis of Piperonylonitrile (3.4-methylenedioxybenzonitrile) from Piperonal (3,4-methylenedioxybenzaldehyde). To a stirred mixture of 200 ml of isopropanol and 1.36 g of cupric chloride at 17-23° C. was added dropwise 58 g (0.487 mole) of 29.4percent aqueous ammonium hydroxide over a period of 190 min. Parallel to the addition of ammonium hydroxide, a solution of 601 g of 99percent piperonal (0.396 mole) and 1.0 g of hexadecane (internal standard) in 100 ml of isopropanol was added over a period of 147 min. Parallel to the additions of ammonium hydroxide and piperonal, 150 g (2.2 moles) of 50percent aqueous hydrogen peroxide was added over a period of 590 min. After the additions were finished, the mixture was worked up by stirring for 1 hour with 10percent aqueous sodium sulfite, and diluted with water and chloroform. The organic layer was separated, the water layer was extracted with chloroform. After evaporation of the solvent, the weight of the crude solid product was 36.4 g (crude yield about 60percent). Recrystallization of the crude from boiling heptane gave 17.9 g of crystalline piperonylonitrile; yield 30.7percent of the theory. With ammonium hydroxide, dihydrogen peroxide in n-heptane, α-n-hexadecene, isopropyl alcohol Patent; Millennium Specialty Chemicals; US6114565; (2000); (A1) English View in Reaxys O

O Br

Rx-ID: 30636237 View in Reaxys 23/117 Yield

Conditions & References

80 %

Stage 1: With magnesium, lithium chloride in tetrahydrofuran, T= 20 °C , Inert atmosphere Stage 2: in tetrahydrofuran, T= 0 - 20 °C , Inert atmosphere Anbarasan, Pazhamalai; Neumann, Helfried; Beller, Matthias; Chemistry - A European Journal; vol. 17; nb. 15; (2011); p. 4217 - 4222 View in Reaxys

0.291 g

Stage 1: With 3-chloroprop-1-ene, trifluoroacetic acid, cobalt(II) dibromide, zinc in acetonitrile, T= 20 °C , Knochel Zinc Vinyl Coupling Stage 2: With zinc in acetonitrile, T= 0 - 50 °C , Inert atmosphere Cai, Yingxiao; Qian, Xin; Rrat, Alice; Auffrant, Audrey; Gosmini, Corinne; Advanced Synthesis and Catalysis; vol. 357; nb. 16-17; (2015); p. 3419 - 3423 View in Reaxys

O O

O– O

Na +

O O

Rx-ID: 33097282 View in Reaxys 24/117 Yield 85 %

Conditions & References With pyridine, hydroxylamine hydrochloride in toluene, Time= 13h, T= 80 °C , Reflux

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Zhu, Jintao; Song, Guangwei; Yao, Guoxin; Chen, Gang; Synthetic Communications; vol. 42; nb. 13; (2012); p. 1934 - 1940 View in Reaxys O

N O

Rx-ID: 18646376 View in Reaxys 25/117 Yield

Conditions & References Reaction Steps: 2 1: 74 percent / 3 h / Ambient temperature 2: 51 percent / HN3, H2SO4 / CHCl3 / 0.08 h / 0 °C With tris-(2-chloro-ethyl)-amine, sulfuric acid in chloroform Sprecher, Milon; Kost, Daniel; Journal of the American Chemical Society; vol. 116; nb. 3; (1994); p. 1016 - 1026 View in Reaxys Reaction Steps: 2 1: benzene; aqueous ammonia 2: phosphorus (V)-chloride With ammonium hydroxide, phosphorus pentachloride, benzene Andrewes; King; Walker; Proceedings of the Royal Society of London, Series B: Biological Sciences; vol. 133; (1946); p. 20,30 View in Reaxys Reaction Steps: 3 1: sodium azide / acetone; water / 0 - 20 °C 2: 1,2-dichloro-ethane / 0.5 h / 80 °C 3: [Ru(p-cymene)2Cl2]; copper (II) acetate monohydrate / 1,2-dichloro-ethane / 80 °C With sodium azide, [Ru(p-cymene)2Cl2], copper (II) acetate monohydrate in water, 1,2-dichloro-ethane, acetone Kumar, Ravi; Arigela, Rajesh K.; Kundu, Bijoy; Chemistry - A European Journal; vol. 21; nb. 33; (2015); p. 11807 - 11812 View in Reaxys

O O

Rx-ID: 35356883 View in Reaxys 26/117 Yield

Conditions & References

76 %

With NH4I, potassium fluoride, Cu(NO3)2 *3H2O, oxygen, Time= 25h, T= 140 °C , Schlenk technique Wang, Zhen; Chang, Sukbok; Organic Letters; vol. 15; nb. 8; (2013); p. 1990 - 1993 View in Reaxys

N 13 C

O N 13C

Rx-ID: 10109356 View in Reaxys 27/117 Yield 60 %

Conditions & References With palladium diacetate, calcium hydroxide powder, triphenylphosphine in N,N-dimethyl-formamide, Time= 40h, T= 90 °C Haajanen, Kati; Botting, Nigel P.; Steroids; vol. 71; nb. 3; (2006); p. 231 - 239 View in Reaxys

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H N

N N

Rx-ID: 5311724 View in Reaxys 28/117 Yield

Conditions & References

91 %

With toluene-4-sulfonic acid in toluene, Time= 0.5h, Heating, Elimination Coskun, Necdet; Arikan, Nevin; Tetrahedron; vol. 55; nb. 40; (1999); p. 11943 - 11948 View in Reaxys N

Rx-ID: 810551 View in Reaxys 29/117 Yield

Conditions & References With acetic anhydride Marcus; Chemische Berichte; vol. 24; (1891); p. 3652 View in Reaxys With acetic anhydride, Behandeln der Reaktionsloesung mit Butylamin oder Pyridin Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1772,1775 View in Reaxys With pyridine, acetyl chloride, T= 0 °C Brady; McHugh; Journal of the Chemical Society; vol. 127; (1925); p. 2421 View in Reaxys With sodium hydroxide, chloroformic acid ethyl ester Brady; McHugh; Journal of the Chemical Society; vol. 123; (1923); p. 1198 View in Reaxys

H N

N O

N Cl

Rx-ID: 2130618 View in Reaxys 30/117 Yield 91 %

Conditions & References With N-(dichloromethylene)-N,N-dimethylammonium chloride in 1,2-dichloro-ethane, 1.) room temp., 1 h, 2.) reflux, 4h Kokel, Bruno; Menichi, Gabriel; Hubert-Habart, Michel; Synthesis; nb. 2; (1985); p. 201 - 202 View in Reaxys

NH 2 S

N O

Rx-ID: 1803011 View in Reaxys 31/117 Yield 56 %

Conditions & References With diphosphorous tetraiodide, triethylamine in benzene, Time= 13h, Heating Suzuki, Hitomi; Tani, Hiroyuki; Takeuchi, Setsuko; Bulletin of the Chemical Society of Japan; vol. 58; nb. 8; (1985); p. 2421 - 2422 View in Reaxys

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O N

Rx-ID: 25997240 View in Reaxys 32/117 Yield 77 %

Conditions & References in water, acetonitrile, Time= 20h, Irradiation Dichiarante, Valentina; Fagnoni, Maurizio; Albini, Angelo; Chemical Communications; nb. 28; (2006); p. 3001 3003 View in Reaxys

N O

Rx-ID: 38750534 View in Reaxys 33/117 Yield 98 %

Conditions & References With 2,2,6,6-tetramethyl-piperidine-N-oxyl, [{Cu(NO3)}(μ-3-(6-(1H-pyrazol-1-yl)pyridin-2-yl)pyrazol-1-ide)]2, oxygen, potassium carbonate, Time= 24h, T= 50 °C Tan, Da-Wei; Xie, Jing-Bo; Li, Qi; Li, Hong-Xi; Li, Jun-Chi; Li, Hai-Yan; Lang, Jian-Ping; Dalton Transactions; vol. 43; nb. 37; (2014); p. 14061 - 14071 View in Reaxys

OH HO

O N

Rx-ID: 41093083 View in Reaxys 34/117 Yield 86 %

Conditions & References With N-iodo-succinimide, phen, 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, 1,1,1,2,2,2-hexamethyldisilane, oxygen, copper diacetate, diisopropylamine, T= 20 - 150 °C , Schlenk technique Zhu, Yamin; Li, Linyi; Shen, Zengming; Chemistry - A European Journal; vol. 21; nb. 38; (2015); p. 13246 - 13252 View in Reaxys O

N O

Rx-ID: 1749294 View in Reaxys 35/117 Yield 16 %, 62 %

Conditions & References With nickel sulphate, ammonium hydroxide, sodium hydroxide, dipotassium peroxodisulfate in water, Time= 6h, Ambient temperature Yamazaki, Shigakazu; Yamazaki, Yasuyuki; Chemistry Letters; nb. 4; (1990); p. 571 - 574 View in Reaxys

62 %, 16 %

With nickel sulphate, ammonium hydroxide, sodium hydroxide, dipotassium peroxodisulfate in water, Time= 6h, Ambient temperature Yamazaki, Shigakazu; Yamazaki, Yasuyuki; Chemistry Letters; nb. 4; (1990); p. 571 - 574 View in Reaxys

H 2N

O O

N O O

Rx-ID: 4763030 View in Reaxys 36/117

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Yield

Conditions & References

95 %

With sodium hypochlorite in ethanol, Time= 0.25h, Ambient temperature Yamazaki, Shigekazu; Synthetic Communications; vol. 27; nb. 20; (1997); p. 3559 - 3564 View in Reaxys

N O O

Rx-ID: 150141 View in Reaxys 37/117 Yield

Conditions & References With potassium hydroxide Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4517 View in Reaxys With sodium ethanolate Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4517 View in Reaxys

O O

N O

O O

Rx-ID: 32757746 View in Reaxys 38/117 Yield 56 %

Conditions & References With NH4I, Cu(NO3)2 *3H2O, oxygen, acetic acid, Time= 18h, T= 130 °C Kim, Jinho; Choi, Jiho; Shin, Kwangmin; Chang, Sukbok; Journal of the American Chemical Society; vol. 134; nb. 5; (2012); p. 2528 - 2531 View in Reaxys

OH HO

N O

O O

Rx-ID: 32757782 View in Reaxys 39/117 Yield 60 %

N HO

O Cl

Rx-ID: 36024007 View in Reaxys 40/117 Yield

Conditions & References

11 %, 89 % Stage 1: With 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical, tert-butylhypochlorite in dichloromethane, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: With ammonia, iodine in dichloromethane, water, Time= 2h, T= 20 °C , Inert atmosphere

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Shimojo, Hiroyuki; Moriyama, Katsuhiko; Togo, Hideo; Synthesis (Germany); vol. 45; nb. 15; (2013); p. 2155 2164; Art.No: SS-2013-F0311-OP View in Reaxys

N N

Rx-ID: 5069828 View in Reaxys 41/117 Yield

Conditions & References

98 %

With potassium carbonate, dimethyl sulfate, Time= 10h, Heating, Elimination Kamal, Ahmed; Arifuddin; Venugopal Rao; Synthetic Communications; vol. 28; nb. 24; (1998); p. 4507 - 4512 View in Reaxys

N Si

Rx-ID: 39717641 View in Reaxys 42/117 Yield

Conditions & References

1.37 g

With [Pip*(O)][BF4] in dichloromethane, Time= 12h, T= 20 °C Kelly, Christopher B.; Lambert, Kyle M.; Mercadante, Michael A.; Ovian, John M.; Bailey, William F.; Leadbeater, Nicholas E.; Angewandte Chemie - International Edition; vol. 54; nb. 14; (2015); p. 4241 - 4245 View in Reaxys

N O O

O N

Rx-ID: 40836271 View in Reaxys 43/117 Yield

Conditions & References

121 mg

With [Ru(p-cymene)2Cl2], copper (II) acetate monohydrate in 1,2-dichloro-ethane, T= 80 °C , regioselective reaction Kumar, Ravi; Arigela, Rajesh K.; Kundu, Bijoy; Chemistry - A European Journal; vol. 21; nb. 33; (2015); p. 11807 - 11812 View in Reaxys N

copper (I)-cyanide O

Rx-ID: 5689416 View in Reaxys 44/117 Yield

Conditions & References With pyridine, T= 220 °C Gensler; Stouffer; Journal of Organic Chemistry; vol. 23; (1958); p. 908 View in Reaxys

N N

Rx-ID: 8671704 View in Reaxys 45/117

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Yield

Conditions & References

83 %

With aluminum oxide, Oxonereg;, Time= 0.0833333h, microwave irradiation Ramalingam; Subba Reddy; Srinivas; Yadav; Synthetic Communications; vol. 30; nb. 24; (2000); p. 4507 - 4512 View in Reaxys

O N

(v1)

Rx-ID: 10025518 View in Reaxys 46/117 Yield

Conditions & References in N,N-dimethyl-formamide, T= 130 °C Suh, Young-Ger; Lee, Yong-Sil; Min, Kyung-Hoon; Park, Ok-Hui; Kim, Jin-Kwan; Seung, Ho-Sun; Seo, SeungYong; Lee, Bo-Young; Nam, Yeon-Hee; Lee, Kwang-Ok; Kim, Hee-Doo; Park, Hyeung-Geun; Lee, Jeewoo; Oh, Uhtaek; Lim, Ju-Ok; Kang, Sang-Uk; Kil, Min-Jung; Koo, Jae-Yeon; Shin, Song Seok; Joo, Yung-Hyup; Kim, Jin Kwan; Jeong, Yeon-Su; Kim, Sun-Young; Park, Young-Ho; Journal of Medicinal Chemistry; vol. 48; nb. 18; (2005); p. 5823 - 5836 View in Reaxys N O

7-oxy-4-methyl-2-<3.4-dioxy-styryl>-benzo-pyrylium chloride

Rx-ID: 16123714 View in Reaxys 47/117 Yield

Conditions & References Reaction Steps: 2 1: 85 percent / ethanol / 1 h / 20 °C 2: 91 percent / TsOH*H2O / toluene / 0.5 h / Heating With toluene-4-sulfonic acid in ethanol, toluene, 1: Condensation / 2: Elimination Coskun, Necdet; Arikan, Nevin; Tetrahedron; vol. 55; nb. 40; (1999); p. 11943 - 11948 View in Reaxys Reaction Steps: 2 1: methanol / 0.25 h / 20 °C 2: 98 percent / K2CO3; dimethyl sulphate / 10 h / Heating With potassium carbonate, dimethyl sulfate in methanol, 1: Addition / 2: Elimination Kamal, Ahmed; Arifuddin; Venugopal Rao; Synthetic Communications; vol. 28; nb. 24; (1998); p. 4507 - 4512 View in Reaxys

N N

H 2N

Rx-ID: 814103 View in Reaxys 48/117 Yield

Conditions & References With diethyl ether, ammonia, KNH2, T= -35 °C , Behandeln des Reaktionsgemisches mit Ammoniumchlorid Hauser; Hoffenberg; Journal of Organic Chemistry; vol. 20; (1955); p. 1535 View in Reaxys NH 2

O O

N O

Rx-ID: 37121470 View in Reaxys 49/117

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Yield

Conditions & References

30 %, 40 %

With SnCl2·2H2O, 1,8-diazabicyclo[5.4.0]undec-7-ene in toluene, Time= 7h, Reflux, Molecular sieve Ganguly, Nemai C.; Nayek, Subhasis; Chandra, Sumanta; Journal of the Indian Chemical Society; vol. 90; nb. 10; (2013); p. 1695 - 1702 View in Reaxys 4

+ -4K

N (v6)

N N

Rx-ID: 39645430 View in Reaxys 50/117 Yield

Conditions & References With N-Methyl-2-pyrrolidone, 1,1'-bis-(diphenylphosphino)ferrocene, palladium diacetate, sodium carbonate, Time= 12h, T= 120 °C , Schlenk technique, Inert atmosphere Yang, Chu-Ting; Han, Jun; Liu, Jun; Gu, Mei; Li, Yi; Wen, Jun; Yu, Hai-Zhu; Hu, Sheng; Wang, Xiaolin; Organic and Biomolecular Chemistry; vol. 13; nb. 9; (2015); p. 2541 - 2545 View in Reaxys N

Rx-ID: 30111253 View in Reaxys 51/117 Yield

Conditions & References Reaction Steps: 2 1: triethylamine / dichloromethane 2: CM-phos; palladium diacetate; potassium carbonate / water / 18 h / 80 °C / Inert atmosphere With CM-phos, palladium diacetate, potassium carbonate, triethylamine in dichloromethane, water Yeung, Pui Yee; So, Chau Ming; Lau, Chak Po; Kwong, Fuk Yee; Angewandte Chemie - International Edition; vol. 49; nb. 47; (2010); p. 8918 - 8922 View in Reaxys

O N

Rx-ID: 40836300 View in Reaxys 52/117 Yield

Conditions & References Reaction Steps: 2 1: 1,2-dichloro-ethane / 0.5 h / 80 °C 2: [Ru(p-cymene)2Cl2]; copper (II) acetate monohydrate / 1,2-dichloro-ethane / 80 °C With [Ru(p-cymene)2Cl2], copper (II) acetate monohydrate in 1,2-dichloro-ethane Kumar, Ravi; Arigela, Rajesh K.; Kundu, Bijoy; Chemistry - A European Journal; vol. 21; nb. 33; (2015); p. 11807 - 11812 View in Reaxys O

O O

N O

Rx-ID: 1749063 View in Reaxys 53/117

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Yield

Conditions & References

65 % Spectr.

With isobutylamine in acetic acid, Time= 2h, T= 50 °C , p= 7500600Torr Azafonov, N. E.; Sedishev, I. P.; Zhulin, V. M.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 39; nb. 4.1; (1990); p. 738 - 741; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 4; (1990); p. 829 - 832 View in Reaxys

65 % Spectr.

With isobutylamine in acetic acid, Time= 2h, T= 50 °C , p= 7500600Torr , other catalysts, other solvents, other pressures, other reaction times, Product distribution Azafonov, N. E.; Sedishev, I. P.; Zhulin, V. M.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 39; nb. 4.1; (1990); p. 738 - 741; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 4; (1990); p. 829 - 832 View in Reaxys N O

Rx-ID: 22375781 View in Reaxys 54/117 Yield

Conditions & References Reaction Steps: 2 1: chloroform; N-bromo-succinimide 2: pyridine / 220 °C With pyridine, N-bromosuccinmide, chloroform Gensler; Stouffer; Journal of Organic Chemistry; vol. 23; (1958); p. 908 View in Reaxys N

Rx-ID: 8613379 View in Reaxys 55/117 Yield

Conditions & References With dihydrogen peroxide, Time= 4h, oxidative dehydrogenation Erman; Snow; Williams; Tetrahedron Letters; vol. 41; nb. 35; (2000); p. 6749 - 6752 View in Reaxys N O

α'-nitro-α-<3.4-methylenedioxy-phenyl>-acetone O

Rx-ID: 5689410 View in Reaxys 56/117 Yield

Conditions & References With sodium nitrite Angeli; Rimini; Gazzetta Chimica Italiana; vol. 25 II; (1895); p. 205 View in Reaxys N O

piperonyloylformic acid O

Rx-ID: 5689422 View in Reaxys 57/117 Yield

Conditions & References With hydroxylamine hydrochloride, water Garelli; Gazzetta Chimica Italiana; vol. 20; (1890); p. 698

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View in Reaxys H N

O O

Rx-ID: 814088 View in Reaxys 58/117 Yield

Conditions & References T= 0 °C , Product distribution Benger; Brady; Journal of the Chemical Society; (1950); p. 1221,1225 View in Reaxys Hauser; Jordan; Journal of the American Chemical Society; vol. 57; (1935); p. 2451; Journal of the American Chemical Society; vol. 58; (1936); p. 1773 View in Reaxys T= 30 °C , Product distribution Benger; Brady; Journal of the Chemical Society; (1950); p. 1221,1225 View in Reaxys Hauser; Jordan; Journal of the American Chemical Society; vol. 57; (1935); p. 2451; Journal of the American Chemical Society; vol. 58; (1936); p. 1773 View in Reaxys

N O

aq.-ethanolic NaOH-solution O N

Rx-ID: 5689415 View in Reaxys 59/117 Yield

Conditions & References T= 0 °C , Kinetics Hauser; Le Maistre; Rainsford; Journal of the American Chemical Society; vol. 57; (1935); p. 1056,1058 View in Reaxys N O

diazotized 3.4-methylenedioxy-aniline

Rx-ID: 5689418 View in Reaxys 60/117 Yield

Conditions & References With anhydrous copper sulphate, sulfuric acid, copper(II) sulfate, Diazotization Mameli; Boi; Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti; vol. <5> 15 II; (1906); p. 104; Gazzetta Chimica Italiana; vol. 36 II; (1906); p. 380 View in Reaxys

N O

H O

Rx-ID: 5689425 View in Reaxys 61/117 Yield

Conditions & References T= 30 °C , spontane Zersetzung, Kinetics Hauser; Gillaspie; Le Maistre; Journal of the American Chemical Society; vol. 57; (1935); p. 567 View in Reaxys

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Hauser; Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4158,4161 View in Reaxys H N O

N O

aqueous sodium carbonate-solution

O O

Rx-ID: 5707792 View in Reaxys 62/117 Yield

Conditions & References T= 0 °C , Product distribution Hauser; Jordan; Journal of the American Chemical Society; vol. 57; (1935); p. 2451; Journal of the American Chemical Society; vol. 58; (1936); p. 1773 View in Reaxys T= 30 °C , Product distribution Hauser; Jordan; Journal of the American Chemical Society; vol. 57; (1935); p. 2451; Journal of the American Chemical Society; vol. 58; (1936); p. 1773 View in Reaxys H

H N

Rx-ID: 814085 View in Reaxys 63/117 Yield

Conditions & References T= 20 °C Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys H

Rx-ID: 814086 View in Reaxys 64/117 Yield

Conditions & References T= 20 °C Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys H N N H

N O

Rx-ID: 814090 View in Reaxys 65/117 Yield

Conditions & References T= 20 °C Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys

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H N

Rx-ID: 814091 View in Reaxys 66/117 Yield

Conditions & References T= 20 °C Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys H N

N O

aqueous ammonia (14n)

Rx-ID: 5707790 View in Reaxys 67/117 Yield

Conditions & References T= 30 °C , Product distribution Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys H N

N O

aqueous ammonia (1n)

Rx-ID: 5707791 View in Reaxys 68/117 Yield

Conditions & References T= 30 °C , Product distribution Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys H N O

N O

ethanolic NaOH-solution

O O

Rx-ID: 5707793 View in Reaxys 69/117 Yield

Conditions & References T= 30 °C , Product distribution Hauser; Sullivan; Journal of the American Chemical Society; vol. 55; (1933); p. 4611 View in Reaxys H N

H 2N

N O

O O

Rx-ID: 814092 View in Reaxys 70/117 Yield

Conditions & References T= 100 °C Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys

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H H

O O

Rx-ID: 5707788 View in Reaxys 71/117 Yield

Conditions & References T= 30 °C , Product distribution Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys H O

sodium carbonate

O O

Rx-ID: 5707794 View in Reaxys 72/117 Yield

ethanolic NaOH-solution

N O

Rx-ID: 5707795 View in Reaxys 73/117 Yield

Conditions & References T= 0 °C Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1772,1775 View in Reaxys H

N O

O O

Rx-ID: 831965 View in Reaxys 74/117 Yield

Conditions & References Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1772,1775 View in Reaxys Rainsford; Hauser; Journal of Organic Chemistry; vol. 4; (1939); p. 480,484, 485, 488, 490 View in Reaxys

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N O

ethanolic KOH-solution O N

Rx-ID: 5689420 View in Reaxys 75/117 Yield

Conditions & References Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4517 View in Reaxys

N O

O– Na +

O N

Rx-ID: 150140 View in Reaxys 76/117 Yield

Conditions & References Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4517 View in Reaxys

Rx-ID: 810552 View in Reaxys 77/117 Yield

Conditions & References Vermillion; Jordan; Hauser; Journal of Organic Chemistry; vol. 5; (1940); p. 75,78 View in Reaxys Vermillion; Hauser; Journal of the American Chemical Society; vol. 62; (1940); p. 2939,2941 View in Reaxys

N O

Rx-ID: 810576 View in Reaxys 78/117 Yield

N Z

H O O

Rx-ID: 833266 View in Reaxys 79/117 Yield

Conditions & References T= 20 °C Rainsford; Hauser; Journal of Organic Chemistry; vol. 4; (1939); p. 480,484, 485, 488, 490

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View in Reaxys

NH 2

N Z

H O O

Rx-ID: 833267 View in Reaxys 80/117 Yield

Conditions & References T= 20 °C Rainsford; Hauser; Journal of Organic Chemistry; vol. 4; (1939); p. 480,484, 485, 488, 490 View in Reaxys N

N N

O O racemate

Rx-ID: 8893180 View in Reaxys 81/117 Yield

Conditions & References Time= 0.366667h, microwave irradiation, Title compound not separated from byproducts Kusurkar; Kannadkar; Synthetic Communications; vol. 31; nb. 15; (2001); p. 2235 - 2239 View in Reaxys

N E

N O

S Cl

Rx-ID: 415133 View in Reaxys 82/117 Yield

Conditions & References Buck; Ide; Journal of the American Chemical Society; vol. 53; (1931); p. 1912,1914 View in Reaxys

N E

Cl O

Rx-ID: 542902 View in Reaxys 83/117 Yield

Conditions & References Buck; Ide; Journal of the American Chemical Society; vol. 54; (1932); p. 3302,3308; Journal of the American Chemical Society; vol. 53; (1931); p. 1912,1914 View in Reaxys

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N E

N O

S Cl

Rx-ID: 591675 View in Reaxys 84/117 Yield

Conditions & References Buck; Ide; Journal of the American Chemical Society; vol. 53; (1931); p. 1912,1914 View in Reaxys

O O

Rx-ID: 810553 View in Reaxys 85/117 Yield

Conditions & References Vermillion; Hauser; Journal of the American Chemical Society; vol. 62; (1940); p. 2939,2941 View in Reaxys

N N

Rx-ID: 814096 View in Reaxys 86/117 Yield

Conditions & References T= 115 °C , Zersetzung, Rate constant Ambrose; Brady; Journal of the Chemical Society; (1950); p. 1243,1246 View in Reaxys T= 139 °C , Zersetzung, Rate constant Ambrose; Brady; Journal of the Chemical Society; (1950); p. 1243,1246 View in Reaxys T= 120 °C , Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys

O O HO

N O

N Z

alkali carbonate

O O

Rx-ID: 5689413 View in Reaxys 87/117 Yield

Conditions & References T= 20 °C Garelli; Gazzetta Chimica Italiana; vol. 21 II; (1891); p. 181 View in Reaxys H

H N H

NH 2

O O

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N O

Rx-ID: 5707801 View in Reaxys 88/117 Yield

Conditions & References in Abhaengigkeit von der Temperatur und vom Loesungsmittel, Product distribution Hauser; Jordan; Journal of the American Chemical Society; vol. 58; (1936); p. 1419,1422 View in Reaxys H N

HO O

Rx-ID: 820305 View in Reaxys 89/117 Yield

Conditions & References T= 120 °C , Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys H

Rx-ID: 372347 View in Reaxys 90/117 Yield

Conditions & References T= 139 °C , Zersetzung, Rate constant Ambrose; Brady; Journal of the Chemical Society; (1950); p. 1243,1246 View in Reaxys H

N O

HO O

Rx-ID: 372539 View in Reaxys 91/117 Yield

Conditions & References T= 120 °C , Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys

Rx-ID: 810554 View in Reaxys 92/117 Yield

Conditions & References T= 0 °C Brady; McHugh; Journal of the Chemical Society; vol. 127; (1925); p. 2421 View in Reaxys

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H Cl

Rx-ID: 814087 View in Reaxys 93/117 Yield

Conditions & References T= 120 °C , Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys H

N O

Rx-ID: 820304 View in Reaxys 94/117 Yield

Conditions & References T= 120 °C , Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys H

N O

Rx-ID: 820306 View in Reaxys 95/117 Yield

Conditions & References T= 120 °C , Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys

copper (I)-cyanide

Rx-ID: 5689417 View in Reaxys 96/117 Yield

Conditions & References Gensler; Stouffer; Journal of Organic Chemistry; vol. 23; (1958); p. 908 View in Reaxys H H

N O

1 mol potassium amide

N O O

O O

Rx-ID: 5707789 View in Reaxys 97/117 Yield

Conditions & References Product distribution Vermillion; Hauser; Journal of Organic Chemistry; vol. 6; (1941); p. 507,508,513,514 View in Reaxys

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H –N

K+

N N

O O

Rx-ID: 5707802 View in Reaxys 98/117 Yield

Conditions & References Vermillion; Hauser; Journal of Organic Chemistry; vol. 6; (1941); p. 507,508,513,514 View in Reaxys

H –N

Na +

N N

O O

Rx-ID: 5707803 View in Reaxys 99/117 Yield

Conditions & References Hauser; Hoffenberg; Journal of Organic Chemistry; vol. 20; (1955); p. 1535 View in Reaxys H N

2,5 mol potassium amide

O NH

N O

H 2N

O O

Rx-ID: 5708519 View in Reaxys 100/117 Yield

Conditions & References Product distribution Hauser; Hoffenberg; Journal of Organic Chemistry; vol. 20; (1955); p. 1535 View in Reaxys

N O

O HO

alkaline permanganate O

Rx-ID: 5689414 View in Reaxys 101/117 Yield

Conditions & References Angeli; Chemische Berichte; vol. 25; (1892); p. 1957; Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti; vol. <5> 1 II; (1892); p. 30 View in Reaxys

N O

diluted acid O

Rx-ID: 5689419 View in Reaxys 102/117 Yield

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H O

Rx-ID: 814089 View in Reaxys 103/117 Yield

Conditions & References Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys O

H N

N O

N N

Rx-ID: 831964 View in Reaxys 104/117 Yield

Conditions & References O-anilinoformyl-β-piperonal oxime Brady; McHugh; Journal of the Chemical Society; vol. 127; (1925); p. 2421 View in Reaxys

N Z

N O

O O

Rx-ID: 5689412 View in Reaxys 105/117 Yield

Conditions & References Garelli; Gazzetta Chimica Italiana; vol. 21 II; (1891); p. 180 View in Reaxys O

N O

hydroxylamine hydrochloride

Rx-ID: 5689421 View in Reaxys 106/117 Yield

Conditions & References Garelli; Gazzetta Chimica Italiana; vol. 20; (1890); p. 698 View in Reaxys NH 2

N O

sodium bicarbonate

Rx-ID: 5689423 View in Reaxys 107/117 Yield

Conditions & References laengere Beruehrung mit der Mutterlauge Robin; Annales de Chimie (Cachan, France); vol. <9> 16; (1921); p. 120 View in Reaxys NH 2

N O

sodium carbonate

Rx-ID: 5689424 View in Reaxys 108/117

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Yield

Conditions & References laengere Beruehrung mit der Mutterlauge Robin; Annales de Chimie (Cachan, France); vol. <9> 16; (1921); p. 120 View in Reaxys

O O

alcoholic NaOH-solution

N O

Rx-ID: 5689426 View in Reaxys 109/117 Yield

Conditions & References β-piperonal oxime O-picryl ether Brady; Klein; Journal of the Chemical Society; vol. 127; (1925); p. 846 View in Reaxys HO

Cl Cl

PCl Cl

5-methyl-3-<3.4-methylenedioxy-phenyl>-1.2.4-oxadiazole

Rx-ID: 5689427 View in Reaxys 110/117 Yield

Conditions & References Behandeln mit Eis oder mit Phosphoroxychlorid und darauf mit Wasser, higher-melting methyl-<3.4-methylenedioxyphenyl>-glyoxime Angeli; Malagnini; Gazzetta Chimica Italiana; vol. 24 II; (1894); p. 141 View in Reaxys O O

N O

N N

Rx-ID: 814083 View in Reaxys 111/117 Yield

Conditions & References Hydrolysis, O-acetyl-β-piperonal oxime Brady; McHugh; Journal of the Chemical Society; vol. 127; (1925); p. 2421 View in Reaxys H N O

O HO

N O

Rx-ID: 814094 View in Reaxys 112/117 Yield

Conditions & References Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys

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N N

Rx-ID: 814099 View in Reaxys 113/117 Yield

Conditions & References Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys H

Rx-ID: 820303 View in Reaxys 114/117 Yield

Conditions & References Zersetzung, Rate constant Brady; Sharawy; Journal of the Chemical Society; (1953); p. 4082,4083 View in Reaxys HO

N Z

N O

O O

Rx-ID: 5689411 View in Reaxys 115/117 Yield

Conditions & References Garelli; Gazzetta Chimica Italiana; vol. 21 II; (1891); p. 180 View in Reaxys O

O HO

N O

Rx-ID: 810577 View in Reaxys 116/117 Yield

Conditions & References La Parola; Gazzetta Chimica Italiana; vol. 73; (1943); p. 94,97 View in Reaxys N O O

Rx-ID: 5689409 View in Reaxys 117/117 Yield

Conditions & References Hettler,H.; Neygenfind,H.; Chemische Berichte; vol. 103; (1970); p. 1397 - 1411 View in Reaxys Vowinkel,E.; Bartel,J.; Chemische Berichte; vol. 107; (1974); p. 1221 - 1227 View in Reaxys Kametani; Takahashi; Ogasawara; Fukumoto; Tetrahedron; vol. 30; nb. 9; (1974); p. 1047 - 1051 View in Reaxys Trabert,C.H.; Archiv der Pharmazie und Berichte der Deutschen Pharmazeutischen Gesellschaft; vol. 294; (1961); p. 246 - 254 View in Reaxys Usui; Yakugaku Zasshi; vol. 89; (1969); p. 689,696; ; vol. 71; nb. 61352; (1969) View in Reaxys

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Knutsen et al.; Journal of Organic Chemistry; vol. 40; (1975); p. 2878 View in Reaxys Brackman; Smit; Recueil des Travaux Chimiques des Pays-Bas; vol. 82; (1963); p. 757,758 View in Reaxys Smith et al.; Journal of Organic Chemistry; vol. 31; (1966); p. 4100 View in Reaxys Deshmukh; Jain; Indian Journal of Chemistry; vol. 6; (1968); p. 337,338 View in Reaxys van Es; Journal of the Chemical Society; (1965); p. 1564 View in Reaxys Albright; Alexander; Organic Preparations and Procedures International; vol. 4; (1972); p. 215 View in Reaxys Vesterager et al.; Tetrahedron; vol. 30; (1974); p. 2509,2510, 2513 View in Reaxys 4.1.1.4.28 Patent; BOEHRINGER INGELHEIM INTERNATIONAL GMBH; HOFFMANN, Matthias; DAHMANN, Georg; FIEGEN, Dennis; HANDSCHUH, Sandra; KLICIC, Jasna; LINZ, Guenter; SCHAENZLE, Gerhard; SCHNAPP, Andreas; EAST, Stephen P.; MAZANETZ, Michael Philip; SCOTT, John; WALKER, Edward; WO2011/92128; (2011); (A1) English View in Reaxys

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