2-Chlorobenzonitrile

Query Query

Results

Date

99 reactions in Reaxys

2017-09-30 14h:29m:43s (EST)

Cl

1. Query

N

Search as: As drawn, No salts, No mixtures, No isotopes, No charges, No radicals

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

1/41

2017-09-30 14:38:13

Cl HO

Cl

N

N

Rx-ID: 2157329 View in Reaxys 1/99 Yield 97 %

Conditions & References With N-trifluoroacetylimidazole in tetrahydrofuran, Time= 3.5h, Heating Keumi, Takashi; Yamamoto, Takayoshi; Saga, Hiroshi; Kitajima, Hidehiko; Bulletin of the Chemical Society of Japan; vol. 54; nb. 5; (1981); p. 1579 - 1580 View in Reaxys

97 %

With cerium(IV) oxide in o-xylene, Time= 0.5h, T= 160 °C , Dean-Stark, Inert atmosphere Rapeyko, Anastasia; Climent, Maria J.; Corma, Avelino; Concepción, Patricia; Iborra, Sara; ACS Catalysis; vol. 6; nb. 7; (2016); p. 4564 - 4575 View in Reaxys

96 %

With phosphoric acid diethyl ester 2-phenylbenzimidazol-1-yl ester, triethylamine in acetonitrile, Time= 0.416667h, T= 20 °C Kokare, Nagnnath D.; Shinde, Devanand B.; Monatshefte fur Chemie; vol. 140; nb. 2; (2009); p. 185 - 188 View in Reaxys

95 %

With thionyl chloride, sodium carbonate in dichloromethane, Time= 1.5h, Heating Kazemi; Kiasat; Javeherian; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 44; nb.

9; (2005); p. 1954 - 1956 View in Reaxys

95 %

4.2.3. 2-Chlorobenzonitrile (Table 2, entry 2) To a 25 mL round-bottom flask equipped with magnetic stirrer were added 2-chlorobenzaldehyde oxime (311 mg, 2 mmol), cupric acetate (Cu(OAc)2) 36 mg (0.2 mmol) and acetonitrile(5 mL). The mixture was heated to reflux for 1.5 h. After cooling to room temperature, the solution was directly evaporated to dryness and the residue was purified by column chromatography on silica gel (ethyl acetate/n-hexane=1:10) to give 2-chlorobenzonitrile as a white solid (261 mg, 95percent). 1H NMR (500 MHz, CDCl3): δ 7.39 (m, 1H), 7.56 (m, 2H), 7.69 (m, 1H) Data are in good agreement with the literature.24 With copper diacetate, acetonitrile, Time= 1.5h, Reflux Ma, Xiao-Yun; He, Ying; Lu, Ting-Ting; Lu, Ming; Tetrahedron; vol. 69; nb. 12; (2013); p. 2560 - 2564 View in Reaxys

94 %

With triphenylphosphine, 2,3-dicyano-5,6-dichloro-p-benzoquinone in dichloromethane, T= 20 °C Aghapour, Ghasem; Amirabadi, Marjan; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 46; nb. 4; (2007); p. 649 - 652 View in Reaxys

94 %

With 1,1,3,3-tetraphenyl-2-oxa-1,3-phoshpinobenzene bis(trifluoromethanesulfonate), triethylamine in dichloromethane, Time= 0.333333h, T= 20 °C Moussa, Ziad; Synthesis; vol. 44; nb. 3; (2012); p. 460 - 468; Art.No: T105811SS View in Reaxys

94 %

With thionyl chloride, captisol® in water, acetone, Time= 0.25h, T= 80 °C , Beckmann Rearrangement Patil, Dipak; Dalal, Dipak; Synthetic Communications; vol. 43; nb. 1; (2013); p. 118 - 128 View in Reaxys

93 %

With 1,8-diazabicyclo[5.4.0]undec-7-ene, p-toluenesulfonyl imidazole in N,N-dimethyl-formamide, Time= 0.25h, Reflux Rad, Mohammad Navid Soltani; Khalafi-Nezhad, Ali; Behrouz, Somayeh; Amini, Zohreh; Behrouz, Marzieh; Synthetic Communications; vol. 40; nb. 16; (2010); p. 2429 - 2440

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

2/41

2017-09-30 14:38:13

View in Reaxys 93 %

With trifluoromethylsulfonic anhydride, triethylamine, triphenylphosphine in dichloromethane, Time= 0.166667h, T= 0 °C Moussa, Ziad; Ahmed, Saleh A.; ElDouhaibi, Ahmad S.; Al-Raqa, Shaya Y.; Tetrahedron Letters; vol. 51; nb. 14; (2010); p. 1826 - 1831 View in Reaxys

92 %

With N-chloro-succinimide, triphenylphosphine in dichloromethane, T= 20 °C Iranpoor; Firouzabadi; Aghapour; Synthetic Communications; vol. 32; nb. 16; (2002); p. 2535 - 2541 View in Reaxys

91 %

With TiCl3(OTf), 1-n-butyl-3-methylimidazolim bromide, Time= 2h Noei, Jalil; Khosropour, Ahmad Reza; Mirjafari, Arsalan; Bulletin of the Korean Chemical Society; vol. 33; nb. 6; (2012); p. 2102 - 2104 View in Reaxys

91 %

1 : 2 Experimental 2.1 Typical procedure for the conversion of 4-nitrobenzaldehyde oxime to 4-nitrobenzonitrile with TCBDA and PPh3 To a mixture of PPh3 (0.315 g, 1.2 mmol) and TCBDA (0.12 g, 0.32 mmol) in dichloromethane (5 mL), 4-nitrobenzaldehyde oxime (0.166 g, 1 mmol) was added. The mixture was stirred at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction (Table 1), the solvent was evaporated. The crude products were purified by short-column chromatography (packed with silica gel, using n-hexane/ethyl acetate (8:2) as eluent) to achieve the desired 4-nitrobenzonitrile with 0.14 g, 95percent yield.

With TCBDA, triphenylphosphine in dichloromethane, T= 20 °C , Reagent/catalyst Ghorbani-Vaghei, Ramin; Shiri, Lotfi; Ghorbani-Choghamarani, Arash; Chinese Chemical Letters; vol. 24; nb.

12; (2013); p. 1123 - 1126 View in Reaxys

90 %

With acetyl chloride, zinc(II) oxide, Time= 0.25h, Heating Sarvari, Mona Hosseini; Synthesis; nb. 5; (2005); p. 787 - 790; Art.No: Z18204SS View in Reaxys

90 %

With 8-bromocaffeine, 1,8-diazabicyclo[5.4.0]undec-7-ene in N,N-dimethyl-formamide, Time= 0.0305556h, 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

90 %

With acetonitrile, Time= 4h, Reflux, Green chemistry Zarghani, Monireh; Akhlaghinia, Batool; Applied Organometallic Chemistry; vol. 29; nb. 10; (2015); p. 683 - 689 View in Reaxys

90 %

With C24H33ClF3N3Os in acetonitrile, Time= 1h, T= 80 °C , Sealed tube Francos, Javier; González-Liste, Pedro J.; Menéndez-Rodríguez, Lucía; Crochet, Pascale; Cadierno, Victorio; Borge, Javier; Antiñolo, Antonio; Fernández-Galán, Rafael; Carrillo-Hermosilla, Fernando; European Journal of Inorganic Chemistry; vol. 2016; nb. 3; (2016); p. 393 - 402 View in Reaxys

89 %

With C8H14N2O4S in dichloromethane, Time= 1h, Reflux Rappai, John P.; Karthikeyan, Jayakumar; Prathapan, Sreedharan; Unnikrishnan, Perupparampil A.; Synthetic Communications; vol. 41; nb. 17; (2011); p. 2601 - 2606 View in Reaxys

89 %

A general procedure for the preparation of nitrile from aldoxime using aceticanhydride as the dehydration agent

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

3/41

2017-09-30 14:38:13

General procedure: K2CO3 (3 mmol) was added to a stirredmixture of aldoxime (1.5 mmol) and 6 mL DMSO, followed by Ac2O (3 mmol).The resulting mixture was stirred at 50 C for a specified period (Table 2). Afterthe reaction was completed, 30 mL water was added then extracted withCH2Cl2 (10 3 mL). The organic phase was washed with water (10 3 mL)then dried with anhydrous Na2SO4. The solvent was evaporated under vacuumto give the nitrile products.

With acetic anhydride, potassium carbonate in dimethyl sulfoxide, Time= 12h, T= 50 °C Song, Yaoping; Shen, Dongguo; Zhang, Qinghua; Chen, Bo; Xu, Guangyu; Tetrahedron Letters; vol. 55; nb. 3; (2014); p. 639 - 641 View in Reaxys 86 %

With MIL-100 (Fe)-NH4F in o-xylene, Time= 2.5h, T= 153 - 160 °C , Dean-Stark, Inert atmosphere Rapeyko, Anastasia; Climent, Maria J.; Corma, Avelino; Concepciõn, Patricia; Iborra, Sara; ChemSusChem; vol. 8; nb. 19; (2015); p. 3270 - 3282 View in Reaxys

85 %

With 1,4-diaza-bicyclo[2.2.2]octane, thionyl chloride in dichloromethane, Time= 1.16667h, T= 20 °C Kazemi; Kiasat; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 42; nb. 6; (2003); p.

1540 - 1543 View in Reaxys

85 %

General procedure for the preparation of nitriles General procedure: PEG-SO2Cl (0.15 mmol, 326 mg) was added to a stirred solution of aldoxime (1.0 mmol) in freshly distilled dichloromethane (10 mL), and the reaction mixture stirred at reflux temperature for the given time in Table 2. After completion of the reaction (monitored by TLC), the solution was concentrated by rotary evaporation and diluted with slow addition of an excess of cold ether with vigorous stirring. The precipitate was filtered through a fritted funnel, washed with ether, and dried well to furnish the PEG-bound sulfonic acid in excellent yield and then converted into the PEG-SO2Cl for the recycling. The filtrate was concentrated in a rotary evaporator, and finally the crude product was purified by column chromatography eluted with 10–20percent ethyl acetate in hexane for their structure analysis.

With poly(ethylene glycol)–bound sulfonyl chloride in dichloromethane, Time= 1.16667h, Reflux Zhang, Xiao-Lan; Liu, Xiao-Ling; Sang, Xiao-Yan; Sheng, Shou-Ri; Synthetic Communications; vol. 47; nb. 3; (2017); p. 232 - 237 View in Reaxys

84 %

With Montmorillonite KSF in toluene, Time= 14h, Heating Meshram; Synthesis; nb. 10; (1992); p. 943 - 944 View in Reaxys

84 %

Preparation of nitriles (4a–4r): General procedure General procedure: To a stirred solution of aldoxime 3 (1.0 mmol) in CH2Cl2 (5 mL)was added PEG-OPCl2 (0.20 mmol, 220 mg) and molecularsieves 4 A (2 wt equiv to aldoxime), the reaction mixture stirred at reuxing temperature for the given time in Table 2. Aftercompletion of the reaction (TLC), diethyl ether (100 mL) wasadded to the reaction mixture with vigorous stirring and thencooled to 0 °C. The recovered white precipitate, along withmolecular sieves 4 A was collected by fltration, washed with cold diethyl ether (2 × 20 mL) for reuse. The combined fltratewas concentrated in a rotary evaporator, and the residue waspurifed by through a pad of silica gel column (10-20percent ethylacetate in hexane) to give pure product, which was characterized by comparison of its IR and 1H NMR spectra or meltingpoint with published13,14,16,18,26,28,30 values. The analytical datafor the obtained products 4a–4r are together with their 1H and13C NMR spectra are presented in the Supplemental Materials(Figures S1– S36).

With Polyethylene glycol supported phosphorus chloride in dichloromethane, Time= 0.666667h, Reflux, Molecular sieve Zhang, Xiao-Lan; Sheng, Shou-Ri; Wei, Mei-Hong; Liu, Xiao-Ling; Phosphorus, Sulfur and Silicon and the Related Elements; vol. 192; nb. 5; (2017); p. 513 - 517 View in Reaxys

80 %

With aluminum oxide, Time= 0.05h, microwave irradiation

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

4/41

2017-09-30 14:38:13

Lingaiah, Nagarapu; Narender, Ravirala; Synthetic Communications; vol. 32; nb. 15; (2002); p. 2391 - 2394 View in Reaxys 80 %

With CTADC in dichloromethane, Time= 4h, Heating Sahu, Sandhyamayee; Patel, Sabita; Mishra, Bijay K.; Synthetic Communications; vol. 35; nb. 24; (2005); p. 3123 - 3126 View in Reaxys

78%

With 1,2-bis(3-fluorophenyl)diselane, dihydrogen peroxide in acetonitrile, Time= 24h, T= 65 °C Yu, Lei; Li, Hongyan; Zhang, Xu; Ye, Jianqing; Liu, Jianping; Xu, Qing; Lautens, Mark; Organic Letters; vol. 16; nb. 5; (2014); p. 1346 - 1349 View in Reaxys

70 %

With carbon disulfide, sodium hydroxide, tetra(n-butyl)ammonium hydrogensulfate in benzene, Time= 0.5h, Ambient temperature Shinozaki, Hiraku; Imaizumi, Mari; Tajima, Moritaka; Chemistry Letters; (1983); p. 929 - 932 View in Reaxys

70 %

With iron(III) sulfate in benzene, Time= 3.5h, Heating, Dehydration Desai; Swami; Mahale; Synthetic Communications; vol. 30; nb. 9; (2000); p. 1623 - 1625 View in Reaxys

27 %

With diethyl chlorophosphate in toluene, Time= 3h, Heating, Beckmann rearrangement Sardarian; Shahsavari-Fard; Shahsavari; Ebrahimi; Tetrahedron Letters; vol. 48; nb. 14; (2007); p. 2639 - 2643 View in Reaxys With 2-(trifluoroacetyloxy)pyridine in tetrahydrofuran, Heating, Yield given Keumi, Takashi; Shimada, Masakazu; Morita, Toshio; Kitajima, Hidehiko; Bulletin of the Chemical Society of Japan; vol. 63; nb. 8; (1990); p. 2252 - 2256 View in Reaxys With 1-[(4-chlorosulfonyl)butyl]-3-methylimidazolium chlorosulfate in acetonitrile, Time= 3h, T= 100 °C Nakajima, Mizuki; Qiao, Kun; Kobayashi, Nobuhisa; Bao, Quanxi; Tomida, Daisuke; Yokoyama, Chiaki; Chemistry Letters; vol. 40; nb. 4; (2011); p. 396 - 397 View in Reaxys With acetic anhydride, Reflux Li, Ziyuan; Ma, Ling; Xu, Jinyi; Kong, Lingyi; Wu, Xiaoming; Yao, Hequan; Chemical Communications; vol. 48; nb. 31; (2012); p. 3763 - 3765 View in Reaxys With phosphorus pentoxide, Time= 2h, Reflux Khan, Khalid Mohammed; Fatima, Itrat; Saad, Syed Muhammad; Taha, Muhammad; Voelter, Wolfgang; Tetrahedron Letters; vol. 57; nb. 5; (2016); p. 523 - 524 View in Reaxys

Cl

Cl N

O

Rx-ID: 2408593 View in Reaxys 2/99 Yield 96 %

Conditions & References 2.3. General procedure General procedure: A mixture of aldehyde (2 mmol), hydroxylamine hydrochloride (3 mmol), and copper oxide NPs (5 molpercent) was placed in a Pyrex cylindrical tube and then homogenized and irradiated at 250 W in a MILESTONE microwave reactor. After irradiation (1-2 min), the mixture was cooled to 25 °C and extracted with dichloromethane (5 ml x 2). The solvent was filtered under vacuum and the organic layer dried over fused calcium chloride.

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

5/41

2017-09-30 14:38:13

The crude product was then subjected to short-column silica gel chromatography using light petrol as an eluent to produce pure product.

With copper(II) oxide, hydroxylamine hydrochloride in neat (no solvent), Time= 0.0208333h, Microwave irradiation, Green chemistry, Mechanism, Reagent/catalyst Anandakumar, Belladamadu Siddappa; Reddy, Muthukur Bhojegowd Madhusudana; Tharamani, Chikka Nagaiah; Pasha, Mohamed Afzal; Chandrappa, Gujjarahalli Thimmanna; Chinese Journal of Catalysis; vol. 34; nb.

4; (2013); p. 704 - 710 View in Reaxys 95 %

With PhNHCO2NH2*TsOH in toluene, Time= 0.5h, Heating, Condensation, elimination Coskun, Necdet; Arikan, Nevin; Tetrahedron; vol. 55; nb. 40; (1999); p. 11943 - 11948 View in Reaxys

94 %

General procedure for the conversion of aldehydes into nitriles with HMBMIBDCI and NH3(aq) General procedure: The mixture of HMBMIBDCI (0.5 mmol, 322 mg) in CH3CN (5 ml) was added into a solution of p-chlorobenzaldehyde (0.5 mmol, 70 mg) in NH3(aq) (1.5 ml) and the resulting dark mixture was stirred for the specified time designated in Table 2 at room temperature. The progress of the reaction was followed by TLC and the dark heterogeneous solution gradually changed to a red solution. To the mixture was added CHCl3 (30 ml) and then the organic phase was washed with an aqueous solution of NaHSO3 (5percent, 20 ml). The organic layer was dried over MgSO4 and evaporated under reduced pressure. The crude material obtained was practically pure in most cases with no need for further purification. Otherwise, the crude products were purified by recrystallization or preparative TLC. All the nitrile products were identified by comparing melting point, 1H, and 13C NMR with those of authentic samples reported in the literature. 2-Chlorobenzonitrile (Table 2, entry 11). Mp 41–43 °C [Ref. [16] mp 42–44 °C]; 1H NMR (400 MHz, CDCl3): δ (ppm) = 7.70 (ddd, J = 7.6, 1.6, 0.4 Hz, 1 H), 7.60–7.53 (m, 2 H), 7.40 (ddd,J = 6.4, 1.6, 0.8 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ (ppm) = 136.92, 134.04, 133.87, 130.07, 127.14, 115.98, 113.45.

With hexamethylene bis(N-methylimidazolium)bis(dichloroiodate), ammonia in water, acetonitrile, Time= 0.833333h, T= 20 °C Hosseinzadeh, Rahman; Golchoubian, Hamid; Nouzarian, Mahboobe; Research on Chemical Intermediates; vol. 41; nb. 7; (2015); p. 4713 - 4725 View in Reaxys

93 %

With hydroxylamine hydrochloride, methanesulfonyl chloride in neat (no solvent), Time= 1.5h, T= 70 °C Khalafi-Nezhad, Ali; Mohammadi, Somayeh; RSC Advances; vol. 4; nb. 27; (2014); p. 13782 - 13787 View in Reaxys

93 %

General procedure: to a solution of 2-pyridinecarbaldehyde 1 (54 mg, 0.5 mmol) and ammonium acetate (385mg, 5.0 mmol) in MeCN )6ml), was added trimethylphenylammonium tribromide (376 mg, 1.0 mmol) at room temperature. after stirring for 21 h at rt, the reaction mixture was treated with 0.5 M aq Na2S2O3(10 ml), 1.0 M NaHCO3 )15 ml) and extracted with EtOAc (60 mL). The organic layer was washed with 0.5 M Na2S2O3 and successively washed with saturated aq.NaCl, and dried over MgSO4.

With ammonium acetate, phenyltrimethylammonium tribromide in acetonitrile, Time= 64h, T= 20 °C Sayama, Shinsei; Heterocycles; vol. 92; nb. 10; (2016); p. 1796 - 1802 View in Reaxys

92 %

With hydroxylamine hydrochloride, toluene-4-sulfonic acid, Time= 0.00972222h, Microwave irradiation Reddy, M. B. Madhusudana; Pasha; Synthetic Communications; vol. 40; nb. 22; (2010); p. 3384 - 3389 View in Reaxys

92 %

With tert.-butylhydroperoxide, ammonium acetate, iodine, sodium carbonate in ethanol, Time= 4.5h, T= 50 °C , Green chemistry Fang, Chaojie; Li, Meichao; Hu, Xinquan; Mo, Weimin; Hu, Baoxiang; Sun, Nan; Jin, Liqun; Shen, Zhenlu; RSC Advances; vol. 7; nb. 3; (2017); p. 1484 - 1489 View in Reaxys

92%

17 : Example 17: Preparation of o-chlorobenzonitrile (Formula (2-3))

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

6/41

2017-09-30 14:38:13

To a 25 mL two-necked round bottom flask equipped with a thermometer and a magnetic stirrer was added 4 mmol of o-chlorobenzaldehyde (Formula (1-3), 6 mmol of NH4OAc, 4 mmol of Na2CO3, 4.4 mmol of TBHP, 0.1 mmol of an I2, 5 mL of absolute ethanol solvent, The reaction flask was then placed in an oil bath which was previously heated to 50 ° C and opened with a magnetic stirrer for 4.5 h. The reaction solution was added The sodium thiosulfate solution is stirred, then extracted with ether, the organic layer is separated, the solvent is distilled off under reduced pressure, and then subjected to column chromatography, The eluent was taken as the eluent with ethyl acetate / petroleum ether volume ratio of 1: 100 as the eluent, and the eluate containing the target compound was collected.

To obtain o-chlorobenzonitrile, the separation yield of 92percent.

With tert.-butylhydroperoxide, ammonium acetate, iodine, sodium carbonate in ethanol, Time= 4.5h, T= 50 °C Patent; Zhejiang University of Technology; Shen Zhenlu; Li Meichao; Fang Chaojie; Mo Weimin; (12 pag.); CN106748881; (2017); (A) Chinese View in Reaxys 91 %

With ammonium acetate, iodine, Time= 0.5h, T= 70 °C Ren, Yi-Ming; Zhu, Yi-Zhong; Cai, Chun; Journal of Chemical Research; nb. 1; (2008); p. 18 - 19 View in Reaxys

91 %

Stage 1: With ammonia in water, Time= 0.166667h, T= 20 °C Stage 2: With tetra-N-butylammonium tribromide in water, Time= 4h, T= 20 °C Zhu, Yi-Zhong; Cai, Chun; Monatshefte fur Chemie; vol. 141; nb. 6; (2010); p. 637 - 639 View in Reaxys

91 %

With potassium hexafluorophosphate, 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, oxygen, 1,1,1,3,3,3-hexamethyl-disilazane, sodium nitrite in acetic acid, acetonitrile, Time= 4h, T= 30 °C , Sealed tube Fang, Chaojie; Li, Meichao; Hu, Xinquan; Mo, Weimin; Hu, Baoxiang; Sun, Nan; Jin, Liqun; Shen, Zhenlu; Advanced Synthesis and Catalysis; vol. 358; nb. 7; (2016); p. 1157 - 1163 View in Reaxys

91 %

With ammonium hydroxide, dihydrogen peroxide, Time= 4h, T= 100 °C , Green chemistry Bhardwaj, Madhvi; Kour, Manmeet; Paul, Satya; RSC Advances; vol. 6; nb. 101; (2016); p. 99604 - 99614 View in Reaxys

90 %

With potassium hydroxide, ammonium bicarbonate, (Bu4N)2S2O8, copper(I) formate, nikel(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

90 %

With aluminum oxide, hydroxylamine hydrochloride, methanesulfonyl chloride, Time= 0.666667h, T= 100 °C Sharghi, Hashem; Sarvari, Mona Hosseini; Tetrahedron; vol. 58; nb. 52; (2002); p. 10323 - 10328 View in Reaxys

90 %

With hydroxylamine hydrochloride, zinc(II) chloride, Time= 0.00777778h, Microwave irradiation, Neat (no solvent) Paesha; Nizam, Aatika; Synthetic Communications; vol. 40; nb. 9; (2010); p. 1276 - 1279 View in Reaxys

90 %

With hydroxylamine hydrochloride, zinc(II) oxide, Time= 0.00972222h, Microwave irradiation, neat (no solvent) Madhusudana Reddy; Pasha; Chinese Chemical Letters; vol. 21; nb. 9; (2010); p. 1025 - 1028 View in Reaxys

90 %

With hydroxylamine hydrochloride, iron(II) sulfate in N,N-dimethyl-formamide, Time= 2.5h, Reflux Patil, Dinanath D.; Wadhava, Gurumeet C.; Deshmukh, Arun K.; Asian Journal of Chemistry; vol. 24; nb. 3; (2012); p. 1401 - 1402 View in Reaxys

89 %

Stage 1: With ammonium hydroxide, potassium iodide in tetrahydrofuran, Time= 0.166667h, T= 20 °C Stage 2: With chloroamine-T in tetrahydrofuran, Time= 4h, T= 20 °C

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

7/41

2017-09-30 14:38:13

Zhu, Yi-Zhong; Zhang, Xi-Quan; Liu, Fei; Gu, Hong-Mei; Zhu, Hai-Liang; Synthetic Communications; vol. 43; nb.

21; (2013); p. 2943 - 2948 View in Reaxys 88 %

With ammonia, sodium methylate, potassium iodide in methanol, T= 5 °C , electrooxidation Okimoto, Mitsuhiro; Chiba, Toshiro; Journal of Organic Chemistry; vol. 53; nb. 1; (1988); p. 218 - 219 View in Reaxys

88 %

With Envirocat EPZGR, hydroxylamine hydrochloride, triethylamine, Time= 0.05h, Irradiation, Reduction Veverkova, Eva; Toma, Stefan; Synthetic Communications; vol. 30; nb. 17; (2000); p. 3109 - 3114 View in Reaxys

88 %

Synthesis of nitriles; general procedure General procedure: An aldehyde (2 mmol), CuO (0.1 mmol), NH2OH·HCl (3 mmol),NaOAc (3 mmol) and acetonitrile (6 mL) were added to a 25 mL round bottom flask equipped with magnetic stirrer. The mixture was heated to reflux for 3–10 h. After cooling to r.t., acetonitrile was distilled off under reduced pressure. Water (15 mL) and ethyl acetate (30 mL) were added to the reaction mixture, and the organic layer was washed with saturated aqueous sodium bicarbonate (1 × 15 mL) and water(1 × 15 mL). The organic layer was dried with Na2SO4, evaporated and the residue was purified by column chromatography on silica gel (ethylacetate/n-hexane) to give the corresponding nitriles. All the nitriles are commercially available and were characterised by 1H NMR spectra,which are available in the ESI. With hydroxylamine hydrochloride, sodium acetate, acetonitrile, copper(II) oxide, Time= 10h, Reflux Ma, Xiaoyun; Ao, Jun; Chen, Zhengjian; Liu, Yi; Journal of Chemical Research; vol. 41; nb. 8; (2017); p. 465 468 View in Reaxys

86 %

General procedure: Preparative electrolysis experiments were performed using 263 APotentiostat/Galvanostat (Princeton Applied Research, USA). 0.1 MNaClO4–CH3CN solution (10 mL) containing aldehydes (1 mmol),TEMPO (0.1 mmol), HMDS (2.5mmol) and AcOH (2.5mmol) was electrolyzedwith stirring in an undivided cell (30 mL) equipped with twoplatinum sheets as anode (1.5 cm2) and cathode (3.0 cm2) respectivelyat a constant potential of 1.5 V vs Ag/Ag+ (0.1MAgNO3 in acetonitrile).The electrode separation was 1 cm. When the reaction was finished,10mL of saturatedNa2SO3 solution was added into the reactionmixtureand stirred for 15 min. Then the mixture was extracted with CH2Cl2(20 mL × 3). The organic layer was dried with anhydrous Na2SO4 andconcentrated in a rotary evaporator. The productswere obtained via purificationof column chromatography and their structures were confirmedby 1H NMR, 13C NMR and MS. NMR was performed on a BrukerAvance III spectrometer. GC-MS was performed on the Thermo TraceISQ instrument with TG 5MS capillary column.

With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, sodium perchlorate, acetic acid, lithium hexamethyldisilazane in acetonitrile, Time= 12h, Electrochemical reaction Chen, Qiguo; Fang, Chaojie; Shen, Zhenlu; Li, Meichao; Electrochemistry Communications; vol. 64; (2016); p. 51 - 55 View in Reaxys

84 %

With 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy, ammonium acetate, sodium perchlorate in acetonitrile, T= 20 °C , Electrolysis Yang, Xianjing; Fan, Zhongquan; Shen, Zhenlu; Li, Meichao; Electrochimica Acta; vol. 226; (2017); p. 53 - 59 View in Reaxys

82 %

With boron trifluoride diethyl etherate, O-(2-aminobenzoyl) hydroxylamine in ethanol, Time= 4h, Heating Reddy, P.S.N.; Reddy, P.Pratar; Synthetic Communications; vol. 18; nb. l6-17; (1988); p. 2179 - 2182 View in Reaxys

82 %

With tert.-butylhydroperoxide, ammonium hydroxide, tetra-(n-butyl)ammonium iodide in water, Time= 12h, T= 80 °C , Catalytic behavior Wang, Liang; Shen, Chen; Wang, Hai-Ping; Zhou, Wei-You; Sun, Fu-An; He, Ming-Yang; Chen, Qun; Journal of Chemical Research; vol. 36; nb. 8; (2012); p. 460 - 462 View in Reaxys

80 %

With hydroxylamine hydrochloride, iodine in dimethyl sulfoxide, T= 20 °C

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

8/41

2017-09-30 14:38:13

Gaikwad, Digambar D.; Renukdas, Sameer V.; Kendre, Babasaheb V.; Shisodia, Suresh U.; Borade, Ravikumar M.; Shinde, Praveen S.; Chaudhary, Sunil S.; Pawar, Rajendra P.; Synthetic Communications; vol. 37; nb. 2; (2007); p. 257 - 259 View in Reaxys 80 %

With pyridine, hydroxylamine hydrochloride, Time= 0.0111111h, Microwave irradiation, neat (no solvent) Pasha; Nizam, Aatika; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 49; nb. 8; (2010); p. 1127 - 1129 View in Reaxys

78 %

With oxygen, acetonitrile, copper(l) chloride in N,N-dimethyl acetamide, Time= 24h, T= 130 °C , Schlenk technique Liu, Lixin; Dong, Jianyu; Zhang, Yaxing; Zhou, Yongbo; Yin, Shuang-Feng; Organic and Biomolecular Chemistry; vol. 13; nb. 39; (2015); p. 9948 - 9952 View in Reaxys

70 %

With phosphorus pentaoxide, phosphoric acid, hydroxylamine hydrochloride in acetic acid, Time= 0.25h, Heating Ganboa, I.; Palomo, C.; Synthetic Communications; vol. 13; nb. 12; (1983); p. 999 - 1006 View in Reaxys

70 %

With pyridine, hydroxylamine hydrochloride, formamide in xylene, Time= 6h, Heating, Condensation Ali, Sayyed Iliyas; Nikalje, Milind D.; Dewkar, Gajanan K.; Paraskar, Abhimanyu S.; Jagtap; Sudalai; Journal of Chemical Research - Part S; nb. 1; (2000); p. 30 - 31 View in Reaxys

25 %

With ammonia, aluminum oxide, copper, T= 320 °C Card, Roger J.; Schmitt, J. Lawrence; Journal of Organic Chemistry; vol. 46; (1981); p. 754 - 757 View in Reaxys Reaction Steps: 2 1: NH2OH*HCl; ZnO / Heating 2: 90 percent / CH3COCl; ZnO / 0.25 h / Heating With hydroxylamine hydrochloride, acetyl chloride, zinc(II) oxide Sarvari, Mona Hosseini; Synthesis; nb. 5; (2005); p. 787 - 790; Art.No: Z18204SS View in Reaxys Reaction Steps: 2 1: water; NH2Cl / 0 °C 2: 275 °C With chloroamine, water Hauser; Hauser; Journal of the American Chemical Society; vol. 52; (1930); p. 2050,2052 View in Reaxys Reaction Steps: 2 1: water; NH2Cl / 0 °C 2: 30 °C / Aufbewahren im Exsiccator ueber NaOH With chloroamine, water Hauser; Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4158,4161 View in Reaxys Reaction Steps: 2 1: hydroxylamine hydrochloride; sodium carbonate / methanol; water / Reflux 2: acetic anhydride / Reflux With hydroxylamine hydrochloride, acetic anhydride, sodium carbonate in methanol, water Li, Ziyuan; Ma, Ling; Xu, Jinyi; Kong, Lingyi; Wu, Xiaoming; Yao, Hequan; Chemical Communications; vol. 48; nb. 31; (2012); p. 3763 - 3765 View in Reaxys Reaction Steps: 2

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

9/41

2017-09-30 14:38:13

1: hydroxylamine hydrochloride; sodium acetate / water; methanol 2: acetic anhydride; potassium carbonate / dimethyl sulfoxide / 12 h / 50 °C With hydroxylamine hydrochloride, sodium acetate, acetic anhydride, potassium carbonate in methanol, water, dimethyl sulfoxide Song, Yaoping; Shen, Dongguo; Zhang, Qinghua; Chen, Bo; Xu, Guangyu; Tetrahedron Letters; vol. 55; nb. 3; (2014); p. 639 - 641 View in Reaxys Reaction Steps: 3 1: ammonia / water / 20 °C / |Green chemistry 2: iodine / water / 20 °C / |Green chemistry 3: ammonia / water / 20 °C / |Green chemistry With ammonia, iodine in water Yadav, Arvind K.; Srivastava, Vishnu P.; Yadav, Lal Dhar S.; Synthetic Communications; vol. 44; nb. 3; (2014); p.

408 - 416 View in Reaxys Reaction Steps: 2 1: hydroxylamine hydrochloride / N,N-dimethyl-formamide / 3 h / |Reflux 2: phosphorus pentoxide / 2 h / |Reflux With phosphorus pentoxide, hydroxylamine hydrochloride in N,N-dimethyl-formamide Khan, Khalid Mohammed; Fatima, Itrat; Saad, Syed Muhammad; Taha, Muhammad; Voelter, Wolfgang; Tetrahedron Letters; vol. 57; nb. 5; (2016); p. 523 - 524 View in Reaxys Reaction Steps: 2 1: hydroxylamine hydrochloride 2: poly(ethylene glycol)–bound sulfonyl chloride / dichloromethane / 1.17 h / |Reflux With hydroxylamine hydrochloride in dichloromethane Zhang, Xiao-Lan; Liu, Xiao-Ling; Sang, Xiao-Yan; Sheng, Shou-Ri; Synthetic Communications; vol. 47; nb. 3; (2017); p. 232 - 237 View in Reaxys Cl

Cl

N H 2N

Rx-ID: 4207953 View in Reaxys 3/99 Yield 98 %

Conditions & References 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

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

90 %

With pyridine, [Pip*(O)][BF4] in dichloromethane, Time= 12h, T= 20 °C , Inert atmosphere Lambert, Kyle M.; Bobbitt, James M.; Eldirany, Sherif A.; Wiberg, Kenneth B.; Bailey, William F.; Organic Letters; vol. 16; nb. 24; (2014); p. 6484 - 6487 View in Reaxys

87 %

With ammonium hydroxide, iodine, Time= 2h, T= 60 °C

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

10/41

2017-09-30 14:38:13

Iida, Shinpei; Togo, Hideo; Tetrahedron; vol. 63; nb. 34; (2007); p. 8274 - 8281 View in Reaxys 87 %

With ammonium hydroxide, iodine, Time= 2h, T= 60 °C Iida, Shinpei; Togo, Hideo; Synlett; nb. 16; (2006); p. 2633 - 2635 View in Reaxys

82 %

With copper(l) iodide, oxygen in dichloromethane, Time= 2h, T= 20 °C , p= 760.051Torr , Sealed tube Xu, Boran; Hartigan, Elizabeth M.; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A.; Angewandte Chemie - International Edition; vol. 55; nb. 51; (2016); p. 15802 - 15806; Angew. Chem.; vol. 128; (2016); p. 16034 - 16038,5 View in Reaxys

75 %

With cis-[Os(VIII)O4(OH)2](2-), [Fe(CN)6](3-), acetonitrile, Time= 1.5h, T= 20 °C Griffith; Suriaatmaja; Canadian Journal of Chemistry; vol. 79; nb. 5-6; (2001); p. 598 - 606 View in Reaxys

74 %

With pyridine, tert.-butylhydroperoxide, iodine, potassium carbonate in water, Time= 0.1h, T= 80 °C Zhang, Jintang; Wang, Zhentao; Wang, Ye; Wan, Changfeng; Zheng, Xiaoqi; Wang, Zhiyong; Green Chemistry; vol. 11; nb. 12; (2009); p. 1973 - 1978 View in Reaxys

72 %

With ammonium hydroxide, 1,3-Diiodo-5,5-dimethyl-2,4-imidazolidinedione, Time= 3h, T= 60 °C Iida, Shinpei; Togo, Hideo; Synlett; nb. 3; (2007); p. 407 - 410 View in Reaxys

70 %

With potassium hydroxide, dipotassium peroxodisulfate, ruthenium trichloride in water, Time= 1h Griffith, William P.; Reddy, Bharti; Shoair, Abdel G. F.; Suriaatmaja, Maria; White, Andrew J. P.; Williams, David J.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); nb. 7; (1998); p.

2819 - 2826 View in Reaxys

61.5 %

General procedure: In a typical process, into a 25 ml autoclave equipped with a magnetic stirrer were added 5percentRu/AC (0.03 mmol, 3 molpercent), benzylamine (1 mmol), 5 mL toluene at room temperature successively. After which the resulting reaction mixture was heated at 150 °C for 4 h under 0.5 MPa of oxygen atmosphere. The final reaction conversion and selectivity towards the corresponding nitriles were determined by Gas Chromatograph. After reaction, the product was purified by column chromatography of the reaction mixture on neutral alumina using hexanes/dichloromethane (80:20) or hexanes/EtOAc (30:1) as eluent.

With 5 active carbon-supported ruthenium, oxygen in toluene, Time= 4h, T= 150 °C , p= 3750.38Torr , Autoclave Niu, Baoqiang; Lu, Fei; Zhang, Hong-Yu; Zhang, Yuecheng; Zhao, Jiquan; Chemistry Letters; vol. 46; nb. 3; (2017); p. 330 - 333 View in Reaxys

17 %

With HRu(1,3-bis(6'-methyl-2'-pyridylimino)isoindoline)(PPh3)2 in toluene, Time= 24h, T= 110 °C , Inert atmosphere, Glovebox, chemoselective reaction Tseng, Kuei-Nin T.; Rizzi, Andrew M.; Szymczak, Nathaniel K.; Journal of the American Chemical Society; vol.

135; nb. 44; (2013); p. 16352 - 16355 View in Reaxys

76 % Spectr.

With iodine, tert-butylamine in acetonitrile, Time= 6h, Ambient temperature Goosen, Andre; McCleland, Cedric W.; Sipamia, Allworth M.; Journal of Chemical Research, Miniprint; nb. 1; (1995); p. 311 - 332 View in Reaxys

78 % Chromat.

With 3 A molecular sieve, oxygen, copper dichloride in toluene, Time= 12h, T= 80 °C , p= 760Torr

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

11/41

2017-09-30 14:38:13

Maeda, Yasunari; Nishimura, Takahiro; Uemura, Sakae; Bulletin of the Chemical Society of Japan; vol. 76; nb.

12; (2003); p. 2399 - 2403 View in Reaxys 99 % Chromat.

With oxygen, RuHAP in toluene, Time= 12h, T= 110 °C Mori; Yamaguchi; Mizugaki; Ebitani; Kaneda; Chemical Communications; nb. 5; (2001); p. 461 - 462 View in Reaxys 5 : Example 5 0.5 ml of o-chlorobenzylamine, 0.05 g of CoAPO-3, 2 ml of 1,4-dioxane was added to a pressure-resistant flask,Mmol of isopropyl hydroperoxide at 30 ° C under normal pressure for 3 hours. The reaction product was analyzed by GC-MS. The amine conversionTo 57percent, nitrile, i.e., o-chlorobenzonitrile, was 93percent selectivity.

With 2-hydroperoxypropane in 1,4-dioxane, Time= 3h, T= 30 °C , p= 760.051Torr Patent; Dalian Institute of Chemical Physics; Wang, Feng; Zhang, Zhe; Xu, Jie; Wang, Min; Zhang, Chaofeng; Chen, Haijun; (7 pag.); CN105085315; (2017); (B) Chinese View in Reaxys

Cl N

Cl

Rx-ID: 5143583 View in Reaxys 4/99 Yield 76 %

Conditions & References 2.3. Catalytic activity The activity of the catalysts for vapor-phase ammoxidation of 2-CLT to 2-CLBN was carried out at atmospheric pressure in a fixedbed,vertical downflow glass reactor placed inside a tubular furnace.The temperature was regulated with the help of energy regulatorsand metered by a thermocouple inserted in the reactor.Fresh catalyst (1.0 g) was charged into the center of the reactorin such a way that the catalyst was sandwiched between two layersof inert glass beads. The reactant 2-chlorotoluene (2-CLT) wasfed using a pressure-equalizing funnel. Air and NH3 were taken from compressed gas cylinders. The flow rates of these gases weremeasured using a manometer. Experiments were carried out in thetemperature range 350–450 C. Reaction products were cooledthrough an ice-cooled condenser and collected in an ice-cooledreceiver. Product analysis was carried out with the help of a gaschromatograph filled with a flame ionization detector and a capillarycolumn.

With 20 V2O5/Al2O3, ammonia, T= 350 °C , p= 760.051Torr , Temperature Dwivedi, Ritambhara; Sharma, Prabhakar; Sisodiya, Akrati; Batra, Manohar Singh; Prasad, Rajendra; Journal of Catalysis; vol. 345; (2017); p. 245 - 257 View in Reaxys With ammonia, oxygen, DC-108, T= 425 °C , Yield given Qiong, Zheng; Chi, Huang; Guangyong, Xie; Chongwen, Xu; Yuanyin, Chen; Synthetic Communications; vol.

29; nb. 13; (1999); p. 2349 - 2354 View in Reaxys 1; 2 :Salicylonitrile synthesis of new technology, the process includes the following steps: (1) 1 part by weight of ochlorotoluene, 1.5 parts by weight of ammonia gas, 1.5 parts by weight of oxygen and 2 parts by weight of water vapor were added to the free turbulent fluidized bed reactor,Was added 1 part by weight and the V-Cr-O 1 part by weight of V-P-O-based fine particles of the mixture as a catalyst, the reaction system raised the temperature to 400 deg.] C; (2) after the end of the reaction, the product within the reactor after cooling the condenser cooling crystallization obtained o-chlorobenzonitrile crude products, and then washed, after distillation to get pure o-chlorobenzonitrile,The remaining ammonia in the reactor is transferred to the neutralization tower containing dilute sulfuric acid for absorption; (3) 1.5 parts by weight was added to o-chlorobenzonitrile pure product obtained in step 2 in a concentration of 15percent of an alkali metal alkoxide solution, controlling the reaction temperature at 170 ,Under normal pressure conditions, after the reaction, to stop heating,Until the temperature inside the system naturally cooled to room temperature,The solvent was recovered by distillation under reduced pressure,And then hydrochloric acid added to the system for acidification, can be obtained purity 95percent, the yield of 93percent salicylonitrile solid;The alkali metal alkoxide solution is a mixture of a methanolic solution of sodium methoxide and an ethanol solution of sodium ethoxide in a weight ratio of 1: 2.

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

12/41

2017-09-30 14:38:13

With ammonia, water, oxygen, T= 400 °C Patent; Anhui Guangxin Agrochemical Co., Ltd.; Huang, Jinxiang; Guo, Xuejun; Wu, Jianping; Hu, Minghong; Yang, Yaming; Cheng, Weijia; Li, Hongwei; Xu, Xiaobing; Gao, Yanbing; Dai, Yuting; (4 pag.); CN106083651; (2016); (A) Chinese View in Reaxys Cl

Cl N

HO

Rx-ID: 9131468 View in Reaxys 5/99 Yield 99 %

Conditions & References 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 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 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, ammonia, oxygen, copper(II) nitrate in water, dimethyl sulfoxide, Time= 7h, T= 80 °C , p= 760.051Torr Tao, Chuanzhou; Liu, Feng; Zhu, Youmin; Liu, Weiwei; Cao, Zhiling; Organic and Biomolecular Chemistry; vol.

11; nb. 20; (2013); p. 3349 - 3354 View in Reaxys

91 %

With Iron(III) nitrate nonahydrate, ammonium hydroxide, 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical in acetonitrile, Time= 12h, T= 20 °C Dighe, Shashikant U.; Chowdhury, Deepan; Batra, Sanjay; Advanced Synthesis and Catalysis; vol. 356; nb. 18; (2014); p. 3892 - 3896 View in Reaxys

90 %

With potassium hydroxide, ammonium bicarbonate, tetrabutylammonium peroxydisulfate, copper(II) formate, nikel(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

90 %

With ammonia, oxygen in tert-Amyl alcohol, water, Time= 24h, T= 130 °C , p= 3750.38Torr Mao, Fei; Qi, Zhengliang; Fan, Haipeng; Sui, Dejun; Chen, Rizhi; Huang, Jun; RSC Advances; vol. 7; nb. 3; (2017); p. 1498 - 1503 View in Reaxys

82 %

3 : Example 3: In the installation of a stirrer, thermometer,In the reaction vessel of the distillation apparatus,3.1 mol of o-chlorobenzyl alcohol (2), 3.9 mol of aniline (3)Mass fraction 65percent nitromethane 310ml, cuprous chloride 1.56mol, mixing evenly,The stirring speed was controlled at 160 rpm, the solution temperature was raised to 115 & lt; 0 & gt;Reaction 5h, Raising the solution temperature to 135 & lt; 0 & gt; C,Reaction 3h,The temperature of the solution was raised to 195 ° C,Reaction 120min,The solution temperature was lowered to 20 & lt; 0 &Adding ammonium nitrate solution 700ml,Mass fraction of 45percent sodium bisulfite solution 130ml, 1.7kPa vacuum distillation,Fractions of 130-135 ° C were collected,Mass fraction of 75percent triethylamine washing,In the mass fraction of 95percent toluene recrystallization,To obtain the crystal o-chlorobenzonitrile 350.80g, yield 82percent.

With aniline, copper(l) chloride in nitromethane, Time= 10h, T= 115 - 195 °C , Temperature, Concentration Patent; Chengdu Chiba Longhua Petroleum Engineering Consulting Co., Ltd; Guan, Genan; (4 pag.); CN105566156; (2016); (A) Chinese View in Reaxys

80 %

With potassium phosphate, ammonium formate in acetonitrile, Time= 16h, T= 115 °C , Sealed tube, Green chemistry

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

13/41

2017-09-30 14:38:13

Molla, Rostam Ali; Ghosh, Kajari; Tuhina; Manirul Islam; New Journal of Chemistry; vol. 39; nb. 2; (2015); p. 921 - 930 View in Reaxys 79 %

With tert.-butylhydroperoxide, ammonia, potassium iodide in water, Time= 15h, T= 60 °C Rajender Reddy; Uma Maheswari; Venkateshwar; Prashanthi; Lakshmi Kantam; Tetrahedron Letters; vol. 50; nb. 18; (2009); p. 2050 - 2053 View in Reaxys

66 %

With ammonium hydroxide, sodium periodate, potassium iodide, Time= 3h, T= 60 °C Zolfigol, Mohammad Ali; Hajjami, Maryam; Ghorbani-Choghamarani, Arash; Bulletin of the Korean Chemical Society; vol. 32; nb. 12; (2011); p. 4191 - 4194 View in Reaxys

35 %

With copper(II) choride dihydrate, 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

50 %Chromat.

With ammonium hydroxide, periodic acid, potassium iodide, Time= 131490h, T= 60 °C , Sealed tube, Green chemistry Ghorbani-Choghamarani, Arash; Sardari, Sara; Zolfigol, Mohammad Ali; Hajjami, Maryam; Synthetic Communications; vol. 43; nb. 1; (2013); p. 52 - 58,7 View in Reaxys Cu(NO3)2-catalysed one-pot synthesis of 5-phenyl-1H-tetrazole directly from benzylic alcohols; general procedure General procedure: Cu(NO3)2·3H2O (0.10 mmol), TEMPO (0.10 mmol), the benzylicalcohol 3 (1.0 mmol) and DMSO (1 mL) were added to a 100 mLround-bottomed flask equipped with a magnetic stirrer. The vesselwas flushed with O2 and aqueous NH3 (25-28percent, 3.0 mmol) was added.The vessel was sealed and the reaction mixture was stirred in an oil bath at 80 °C for 8 h. After cooling to room temperature, the stopper wasremoved and NaN3 (2.0 mmol) was added. Stirring was continued in anoil bath at 120 °C for 16 h. After completion of the reaction, the reactionwas acidified HCl (3 M, pH 1.0). Ethyl acetate (~30 mL) was added,and the mixture was stirred until no solid was present. The organiclayer was separated, and the aqueous layer was extracted with ethylacetate twice. The combined organic layers were washed with saturatedbrine, and concentrated in vacuo. The residue was purified by columnchromatography (silica gel, EtOAc-PE) to afford the product 2.

With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, copper(II) nitrate trihydrate, ammonia, oxygen in water, dimethyl sulfoxide, Time= 24h, T= 80 °C , p= 760.051Torr , Sealed tube Tao, Chuanzhou; Wang, Bin; Sun, Lei; Yi, Jiuyin; Shi, Dahua; Wang, Jian; Liu, Weiwei; Journal of Chemical Research; vol. 41; nb. 1; (2017); p. 25 - 29 View in Reaxys

Cl

Cl

N N

Cl

H 2N

Cl

Rx-ID: 45552941 View in Reaxys 6/99 Yield 72 %

Conditions & References Typical procedures for Cu-catalyzed aerobic oxidation of primary amines with air for nitrile synthesis: General procedure: A mixture of benzylamine 1a (107.0 mg, 1.0 mmol), CuCl (5.0 mg, 0.05 mmol, 5 molpercent), 2,2,6,6-tetramethyl-1-piperidyloxy (TEMPO, 7.8 mg, 0.05 mmol, 5 molpercent), and N,N-dimethylethane-1,2-diamine (DMEDA, 4.4 mg, 0.05 mmol, 5 molpercent) in toluene (0.5 mL) sealed in a Schlenk tube (100 mL) with an air balloon was stirred at 80 °C for 24 h. The reaction was then monitored by TLC and/or GC-MS. After completion of the reaction, solvent was evaporated under vacuum. The residue was purified by scosh column chromatography on silica gel using petroleum ether and ethyl acetate (0–100/1) as the eluent, giving product 2a in 80percent isolated yield

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

14/41

2017-09-30 14:38:13

With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, N,N-dimethylethylenediamine, copper(l) chloride in toluene, Time= 24h, T= 80 °C , Sealed tube, Schlenk technique, chemoselective reaction Ma, Xian-Tao; Xu, Hao; Xiao, Ying-Lin; Su, Chen-Liang; Liu, Jian-Ping; Xu, Qing; Chinese Chemical Letters; vol. 28; nb. 6; (2017); p. 1336 - 1339 View in Reaxys HO N

Cl N

Rx-ID: 103124 View in Reaxys 7/99 Yield

Conditions & References

76.3 %

Syntheses of Compounds (a-g) General procedure: A mixture of phenols (100.0 mmol) phenylphosphonic dichloride (11.0 mmol) and phosphorus pentachloride (110.0 mmol) was slowly heated to 160 °C while distilled the byproduct POCl3. And the mixture was stirred at the same temperature for 5 hours. TLC analysis showed the reaction had been finished. The POCl3 was evaporated in vacuum and the residue was poured into ice water, and it was neutralized with saturated aqueous sodium carbonate solution, and extracted with acetic ether. The organic layer was washed with water, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure, the obtained crude product was distilled or purified with silica gel chromatography, the target compound was obtained. The structures of compounds were confirmed by MS and 1H NMR data which were listed as follows.

With P,P-dichlorophenylphosphine oxide, phosphorus pentachloride, Time= 5h, T= 160 °C Wu, Jiang; Zhou, Junpeng; Shi, Yalei; Zhu, Jintao; Synthetic Communications; vol. 46; nb. 19; (2016); p. 1619 1624 View in Reaxys With phosphorus pentachloride Pfeiffer; Engelhardt; Alfuss; Justus Liebigs Annalen der Chemie; vol. 467; (1928); p. 171 View in Reaxys Cl

Cl H 2N

N O

Rx-ID: 667296 View in Reaxys 8/99 Yield 95 %

Conditions & References With trimethylsilyl methanesulfonate, phosphorus pentoxide, Time= 3h, T= 70 - 75 °C , further reagents Rao, C. Someswara; Rambabu, M.; Srinivasan, P. S.; Synthetic Communications; vol. 19; nb. 7,8; (1989); p. 1431 - 1436 View in Reaxys

93 %

With triethylamine, trifluoroacetyl chloride in dichloromethane Saednya, Akbar; Synthesis; nb. 2; (1985); p. 184 - 185 View in Reaxys

93 %

With C8H14N2O4S in dichloromethane, Time= 1h, Reflux Rappai, John P.; Karthikeyan, Jayakumar; Prathapan, Sreedharan; Unnikrishnan, Perupparampil A.; Synthetic Communications; vol. 41; nb. 17; (2011); p. 2601 - 2606 View in Reaxys

91 %

With trichloromethyl chloroformate in various solvent(s), 0-5 deg C then heated to 60 deg C, 5 min Mai, Khuong; Patil, Ghanshyam; Tetrahedron Letters; vol. 27; nb. 20; (1986); p. 2203 - 2206 View in Reaxys

91 %

With trimethylsilylphosphate, Time= 0.5h, Heating

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

15/41

2017-09-30 14:38:13

Yokoyama, Masataka; Yoshida, Sayaka; Imamoto, Tsuneo; Synthesis; nb. 7; (1982); p. 591 - 592 View in Reaxys 88 %

With vanadium oxide on hydrotalcite (V/HT) in 1,3,5-trimethyl-benzene, Time= 24h, Reflux Sueoka, Shoichiro; Mitsudome, Takato; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi; Chemical Communications; vol. 46; nb. 43; (2010); p. 8243 - 8245 View in Reaxys

88 %

2.2. General procedure for the dehydration of amides to nitriles General procedure: To a 25ml Schlenk tube containing a solution of 1 in 2ml of THF was added amide (1.0 mmol) and (EtO)3SiH (0.50 g, 3.0 mmol). The reaction mixture was stirred at 60 °C until there was no amide left (monitored

by TLC and GC-MS). The product was purified according to literature procedures by Beller [27].

With Triethoxysilane, [cis-Fe(H)(SPh)(PMe3)4] in tetrahydrofuran, Time= 24h, T= 60 °C , Inert atmosphere Xue, Benjing; Sun, Hongjian; Wang, Yan; Zheng, Tingting; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter; Catalysis Communications; vol. 86; (2016); p. 148 - 150 View in Reaxys

85 %

With pyridine, phenyl chloroformate in dichloromethane, T= 0 - 20 °C Bose; Varadarajan; Vanajatha; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 40; nb. 8; (2001); p. 722 - 723 View in Reaxys With trichloromethyl chloroformate in tetrahydrofuran, Time= 4h, Heating, investigation of the solvent effect of various solvents for the dehydration Mai, Khuong; Patil, Ghanshyam; Tetrahedron Letters; vol. 27; nb. 20; (1986); p. 2203 - 2206 View in Reaxys With thionyl chloride Borsche; Scriba; Justus Liebigs Annalen der Chemie; vol. 541; (1939); p. 283,290 View in Reaxys With aluminium trichloride, sodium chloride Norris; Klemka; Journal of the American Chemical Society; vol. 62; (1940); p. 1432,1434 View in Reaxys With aminosulfonic acid, T= 220 °C Kirsanow; Solotow; Zhurnal Obshchei Khimii; vol. 20; (1950); p. 284,287; ; (1950); p. 6384 View in Reaxys

84 % Chromat.

With sodium tetrahydroborate in diethylene glycol dimethyl ether, Time= 2h, T= 162 °C Zhu, Hua-Jie; Lu, Kai-Tao; Sun, Guang-Ri; He, Jin-Bao; Li, Hai-Qing; Pittman Jr., Charles U.; New Journal of Chemistry; vol. 27; nb. 2; (2003); p. 409 - 413 View in Reaxys Cl

N

Rx-ID: 6520242 View in Reaxys 9/99 Yield 99 %

Conditions & References 9 :General procedure: With respect to 2 mmol of each alcohol represented by the general formula (1), 4 ml of CH 2 Cl 2 as a solvent, 0.05 equivalent of TEMPO as an N-nitrosyl compound, (A) t-BuOCl, (B) I 2 or (C ) N, N'-diiodo-5,5dimethylhydantoin (DIH) were mixed in a predetermined amount and stirred for a predetermined time at room temperature.Next, 1.5 equivalents of I 2 and 4 ml of aqueous ammonia were added, and the mixture was stirred at room temperature for 2 hours.

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

16/41

2017-09-30 14:38:13

Stage 1: With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical, tert-butylhypochlorite in dichloromethane, Time= 0.5h, T= 20 °C Stage 2: With ammonium hydroxide, iodine in dichloromethane, Time= 2h, T= 20 °C , Reagent/catalyst Patent; CHIBA UNIVERSITY; GODO SHIGEN COMPANY LIMITED; TOGO, HIDEO; SHIMOJO, HIROYUKI; MORIYAMA, KATSUHIKO; MIYAMOTO, MICHIHIKO; (16 pag.); JP2015/40203; (2015); (A) Japanese View in Reaxys 93 %

12.1 :General procedure: phenylacetic acid or its derivative (0.5mmol), Cu(TFA)2(20mmolpercent), urea (1.5 mmol) was added to the pressure sealed tube containing (0.75mL) of DMSO, after filling oxygen at 130 stirred for about 20h, the process by TLC and GC tracking (specifically the reaction time is determined by GC and TLC tracking results). After the raw material was observed by the GC and TLC the reaction has been completed the reaction, the reaction was removed, cooled to room temperature.To the reaction was added 20mL of ethyl acetate, washed with NaHCO3(20mL × 2), washed with saturated brine 20mL.The combined aqueous phases with ethyl acetate (20mL × 2) after stripping the combined organic phases with anhydrous sodium sulfate. The organic phase was dried by rotary evaporator spin solvent, product was purified by silica gel column, eluent ratio of ethyl acetate: petroleum ether = 50: 1. Benzonitrile obtained in a yield of 84percent.

With oxygen, copper(II) trifluoroacetate in dimethyl sulfoxide, Time= 26h, T= 110 °C , Sealed tube, Green chemistry Patent; Huaqiao University; Song, Qiuling; Feng, Qiang; (8 pag.); CN103772236; (2016); (B) Chinese View in Reaxys

75 %

7; 8 Patent; Jimenez, Leslie S.; Ramanathan, Ahalya; US2010/331566; (2010); (A1) English View in Reaxys TRABERT; Archiv der Pharmazie; vol. 294 /66; (1961); p. 246 - 254 View in Reaxys Fizet,C.; Streith,J.; Tetrahedron Letters; (1974); p. 3187 - 3188 View in Reaxys Kanaoka et al.; Chemical and Pharmaceutical Bulletin; vol. 18; (1970); p. 397,398 View in Reaxys Luecke; Winter; Chimia; vol. 25; (1971); p. 94 View in Reaxys Ikeda et al.; Synthesis; (1978); p. 301 View in Reaxys Streith et al.; Helvetica Chimica Acta; vol. 59; (1976); p. 2786,2790 View in Reaxys Sonobe; Kogyo Kagaku Zasshi; vol. 70; (1967); p. 2305,2307 View in Reaxys Patent; Pfizer Inc.; US3706747; (1970); ; vol. 78; nb. 72187 View in Reaxys Nakagawa; Tsuji; Chemical and Pharmaceutical Bulletin; vol. 11; (1963); p. 296,297 View in Reaxys Smith; Walker; Journal of Organic Chemistry; vol. 27; (1962); p. 4372,4373 View in Reaxys Glass; Hoy; Tetrahedron Letters; (1976); p. 1781 View in Reaxys Suvorov et al.; Zhurnal Organicheskoi Khimii; vol. 6; (1970); p. 1219,1225 View in Reaxys Cassar; Journal of Organometallic Chemistry; vol. 54; (1973); p. C57 View in Reaxys Patent; BASF A.G.; FR1525498; (1966); ; vol. 71; nb. 80992d; (1969) View in Reaxys Patent; Hoechst; DE2239799; (1974); ; vol. 80; nb. 133086 View in Reaxys Patent; BASF; DE2310184; (1974); ; vol. 82; nb. 4041 View in Reaxys Patent; Jpn. Chem. Ind.; DE1230026; (1966); ; vol. 66; nb. 55255 View in Reaxys Suleimanow et al.; Azerbaidzhanskii Khimicheskii Zhurnal; vol. 1; (1976); p. 36; ; vol. 85; nb. 159604; (1976)

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

17/41

2017-09-30 14:38:13

View in Reaxys Olah; Keumi; Synthesis; (1979); p. 112 View in Reaxys Norman; Radda; Journal of the Chemical Society; (1961); p. 3610 View in Reaxys Sakanishi; Ogata; Bulletin of the Chemical Society of Japan; vol. 42; (1969); p. 2502,2503 View in Reaxys Urano et al.; Yuki Gosei Kagaku Kyokaishi; vol. 30; (1972); p. 154,158,159 View in Reaxys Hodgkins; King; Journal of the American Chemical Society; vol. 85; (1963); p. 2679,2680 View in Reaxys Crawford; Woo; Canadian Journal of Chemistry; vol. 43; (1965); p. 3178,3187 View in Reaxys Gruenanger; Langella; Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti; vol. 36; nb. 3; (1964); p. 387,388-390; ; vol. 62; nb. 3973g; (1965) View in Reaxys Becke; Burger; Justus Liebigs Annalen der Chemie; vol. 716; (1968); p. 78 View in Reaxys Examples of aromatic nitriles (I) which can be prepared by the process according to the present invention are: para-chloro-benzonitrile; meta-chloro-benzonitrile; ortho-chloro-benzonitrile; 2-fluoro-benzonitrile; 2,3-di-chloro-benzonitrile; 3,4-di-chloro-benzonitrile; 2,3,4-tri-chloro-benzonitrile; 2,4,5-tri-chloro-benzonitrile; 3,4,5-tri-chloro-benzonitrile; ...

Patent; ENICHEM SYNTHESIS S.p.A.; EP441004; (1991); (A1) English View in Reaxys Process according to claim 1, characterized in that the following nitriles (I) are prepared: para-chloro-benzonitrile; meta-chloro-benzonitrile; ortho-chloro-benzonitrile; 2-fluoro-benzonitrile; 2,3-di-chloro-benzonitrile; 3,4-di-chloro-benzonitrile; 2,3,4-tri-chloro-benzonitrile; 2,4,5-tri-chloro-benzonitrile; 3,4,5-tri-chloro-benzonitrile; ...

Patent; ENICHEM SYNTHESIS S.p.A.; EP441004; (1991); (A1) English View in Reaxys Cl N

Cl

O N

HO

Rx-ID: 36713507 View in Reaxys 10/99 Yield 97 %

Conditions & References Time= 0.416667h, T= 350 °C , p= 48754.9Torr , Supercritical conditions, Flow reactor Cantillo, David; Kappe, C. Oliver; Journal of Organic Chemistry; vol. 78; nb. 20; (2013); p. 10567 - 10571 View in Reaxys

28 %

General procedure: General procedure for the reaction of acetonitrilewith carboxylic acids. A 17-mL stainless-steelhigh-pressure microreactor was charged with 1 mmolof Mo(CO)6 or VO(acac)2, 100 mmol of carboxylicacid, 500 mmol of acetonitrile, and 50 mmol of carbontetrachloride. The reactor was hermetically closed andheated for 6 h at

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

18/41

2017-09-30 14:38:13

150°C. When the reaction wascomplete, the reactor was cooled to room temperatureand opened, the mixture was filtered through a layer ofAl2O3, unreacted acetonitrile and carbon tetrachloridewere distilled off, and the residue was distilled underatmospheric or reduced pressure or recrystallized fromethanol.

With molybdenum hexacarbonyl in tetrachloromethane, Time= 6h, T= 150 °C , Autoclave Khusnutdinov; Shchadneva; Bayguzina; Mayakova, Yu. Yu.; Russian Journal of Organic Chemistry; vol. 52; nb.

9; (2016); p. 1282 - 1286; Zh. Org. Khim.; vol. 52; nb. 9; (2016); p. 1295 - 1299,5 View in Reaxys 4

+ -4K

N

Cl

N

Cl

N (v6)

N

I

N

Fe N N

Rx-ID: 38673590 View in Reaxys 11/99 Yield

Conditions & References

93 %

With mesoporous silica SBA-15 supported Cu2O nanoparticles in N,N-dimethyl-formamide, Time= 8h, T= 120 °C , Green chemistry Yin, Wenzhu; Liu, Rui; He, Guangke; Lv, Wangjie; Zhu, Hongjun; RSC Advances; vol. 4; nb. 71; (2014); p.

37773 - 37778 View in Reaxys

26 %

17 : Example 17: Photocatalytic synthesis of compound 2-chlorobenzonitrile In a 25 mL screw test tube, 0.25 mmol of 2-chloroiodobenzene, 0 l mmol of cyanoating agent K4 [Fe (CN) 6], sodium acetate 0 · 25 mmol, 100 mg 3 wtpercent Pd / CeO2, and then 7 mL of N, N-dimethylformamide and lmL isopropanol were mixed with Machine solvent to test tube, 500W visible light irradiation under the magnetic stirring reaction, control visible light intensity of 0.74W / cm2, the reaction Temperature of 55 ° C, 12 hours after the reaction to stop the reaction, take a small amount of reaction solution by microporous membrane filtration, methanol solvent dilution The samples were tested in liquid phase. The samples to be tested were compared with the 2-chloroiodobenzene standard and the 2-chlorobenzonitrile standard. The conversion of the reaction substrate was 41.2percent, the selectivity of the target product was 72.1percent, and the liquid product yield was 29.7percent. Post-processing Method for washing with a cloth funnel filter catalyst, drying for recycling use; reaction solution by dichloromethane and water mixture After the solution was extracted, the organic layer was concentrated and the final product 2-chlorobenzonitrile was obtained by column chromatography. The isolated yield was 26percent With 3 Pd/CeO2, sodium acetate in N,N-dimethyl-formamide, isopropyl alcohol, Time= 12h, T= 55 °C , Irradiation Patent; Nanjing University of Technology; Guo, Cheng; Gong, Xubin; Wu, Lou; Li, Qing; Wang, Jianjiang; (11 pag.); CN105777579; (2016); (A) Chinese View in Reaxys Cl

Cl

O N

Rx-ID: 41758405 View in Reaxys 12/99 Yield

Conditions & References

72 %

With aluminum (III) chloride, sodium nitrite in N,N-dimethyl-formamide, Time= 8h, T= 90 °C , Schlenk technique Ge, Jing-Jie; Yao, Chuan-Zhi; Wang, Mei-Mei; Zheng, Hong-Xing; Kang, Yan-Biao; Li, Yadong; Organic Letters; vol. 18; nb. 2; (2016); p. 228 - 231 View in Reaxys

Cl

Cl

Cl N

HO

O

Rx-ID: 42199580 View in Reaxys 13/99

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

19/41

2017-09-30 14:38:13

Yield

Conditions & References With [2,2]bipyridinyl, ammonium hydroxide, copper(l) iodide, N,N-dimethyl-(4-(2,2,6,6-tetramethyl-1-oxyl-4-piperidoxyl)butyl)dodecylammonium bromide, oxygen in neat (no solvent), Time= 9h, T= 55 °C , p= 750.075Torr , Green chemistry, Overall yield = 61.6 percent Zhang, Yuecheng; Huang, Rong; Gao, Baosheng; Zhao, Jiquan; Catalysis Letters; vol. 146; nb. 1; (2016); p. 220 - 228 View in Reaxys Cl

Cl

N

Rx-ID: 42735682 View in Reaxys 14/99 Yield

Conditions & References

51 %

2. Typical procedure for the synthesis of nitriles from olefins General procedure: A Schlenk tube was charged with olefins 1 (0.4 mmol), NaNO2 (138 mg, 2 mmol), HCOOH (0.5 mL, 10 mmol), and CH3CN(4.5mL). The reaction mixture was stirred at 70 °C under air atmosphere for 4 h. After cooling to room temperature, the solution was filtered to remove the solid by-product then was washed with ethyl acetate (3×10 mL). The solution was concentrated under vacuum and purified by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate) to obtain the desired product 2.

With formic acid, sodium nitrite in acetonitrile, Time= 4h, T= 70 °C , Schlenk technique Liu, Qiang; Fang, Bao; Bai, Xiaohui; Liu, Yuan; Wu, Yao; Xu, Guiming; Guo, Cancheng; Tetrahedron Letters; vol. 57; nb. 24; (2016); p. 2620 - 2623 View in Reaxys Cl

Cl

N O

Rx-ID: 43205215 View in Reaxys 15/99 Yield

Conditions & References

69 %

With oxygen, copper(l) cyanide in dimethyl sulfoxide, T= 150 °C Gu, Lijun; Jin, Cheng; Zhang, Hongtao; Liu, Jiyan; Li, Ganpeng; Yang, Zhi; Organic and Biomolecular Chemistry; vol. 14; nb. 28; (2016); p. 6687 - 6690 View in Reaxys HO N

Cl

O N

HO

Rx-ID: 43737377 View in Reaxys 16/99 Yield 75 %

Conditions & References General procedure: General procedure for the reaction of acetonitrilewith carboxylic acids. A 17-mL stainless-steelhigh-pressure microreactor was charged with 1 mmolof Mo(CO)6 or VO(acac)2, 100 mmol of carboxylicacid, 500 mmol of acetonitrile, and 50 mmol of carbontetrachloride. The reactor was hermetically closed andheated for 6 h at 150°C. When the reaction wascomplete, the reactor was cooled to room temperatureand opened, the mixture was filtered through a layer ofAl2O3, unreacted acetonitrile and carbon tetrachloridewere distilled off, and the residue was distilled underatmospheric or reduced pressure or recrystallized fromethanol.

With tetrachloromethane, bis(acetylacetonate)oxovanadium, Time= 6h, T= 150 °C , Autoclave Khusnutdinov; Shchadneva; Bayguzina; Mayakova, Yu. Yu.; Russian Journal of Organic Chemistry; vol. 52; nb.

9; (2016); p. 1282 - 1286; Zh. Org. Khim.; vol. 52; nb. 9; (2016); p. 1295 - 1299,5 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

20/41

2017-09-30 14:38:13

O

N O

Cl

Cl

O

N

O

I

Rx-ID: 44061850 View in Reaxys 17/99 Yield

Conditions & References

94 %

With potassium phenolate, palladium diacetate, potassium carbonate, dimethyl cis-but-2-ene-1,4-dioate, triphenylphosphine in N,N-dimethyl-formamide, Time= 24h, T= 120 °C , Schlenk technique, Inert atmosphere Maestri, Giovanni; Cañeque, Tatiana; Della Ca, Nicola; Derat, Etienne; Catellani, Marta; Chiusoli, Gian Paolo; Malacria, Max; Organic Letters; vol. 18; nb. 23; (2016); p. 6108 - 6111 View in Reaxys

O

N O

Cl

Cl

O

N

O

Br

Rx-ID: 44061858 View in Reaxys 18/99 Yield

Conditions & References

78 %

With potassium phenolate, palladium diacetate, potassium carbonate, dimethyl cis-but-2-ene-1,4-dioate, triphenylphosphine in N,N-dimethyl-formamide, Time= 24h, T= 120 °C , Schlenk technique, Inert atmosphere Maestri, Giovanni; Cañeque, Tatiana; Della Ca, Nicola; Derat, Etienne; Catellani, Marta; Chiusoli, Gian Paolo; Malacria, Max; Organic Letters; vol. 18; nb. 23; (2016); p. 6108 - 6111 View in Reaxys

Cl

Cl

N

O

N

I

Rx-ID: 39376037 View in Reaxys 19/99 Yield

Conditions & References

58 %

With tert.-butylhydroperoxide, copper(II) nitrate trihydrate, water, acetic acid, Time= 40h, T= 140 °C , chemoselective reaction Zhang, Lianpeng; Lu, Ping; Wang, Yanguang; Chemical Communications; vol. 51; nb. 14; (2015); p. 2840 - 2843 View in Reaxys

Cl

Cl

Cl N

O

O

Cl

Rx-ID: 39755364 View in Reaxys 20/99 Yield

Conditions & References

60 %, 52 %

With sodium azide, CuCl2·2H2O, oxygen in DMFA, Time= 10h, T= 100 °C , Schlenk technique, Sealed tube Gu, Lijun; Jin, Cheng; Chemical Communications; vol. 51; nb. 30; (2015); p. 6572 - 6575 View in Reaxys Cl

HO

Cl

Cl

N

N Cl

N Cl

Rx-ID: 41313856 View in Reaxys 21/99 Yield

Conditions & References With methyltriethylammonium methylsulfate in acetonitrile, T= 20 °C , Electrolysis Hartmer, Marius F.; Waldvogel, Siegfried R.; Chemical Communications; vol. 51; nb. 91; (2015); p. 16346 - 16348 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

21/41

2017-09-30 14:38:13

Cl

S

Cl

NH

N

O

S

N

Rx-ID: 41483102 View in Reaxys 22/99 Yield

Conditions & References

102 g, 93.5 1.b; 1.c; 1.d : Example 1 %, 210 g According to step b) 381 g of the organic layer, comprising 2-(octadecylthio)benzonitrile (IV) obtained in step a), 100 g of chlorobenzene and 32 g of water are added into a 1000 ml four-necked flask with a stirrer, a thermometer and a condenser. At a temperature in the range of from 20 to 30° C., 53 g chlorine are blown into the mixture over a period of 2 hours. The mixture is further heated to a temperature in the range of from 60 to 65° C. and then allowed to further react for 1 h. During the reaction the reaction mixture (RM) is formed. After completion of the reaction the reaction mixture (RM) is cooled to a temperature in the range of from 20 to 30° C. and according to step c) 200g of water are added to the reaction mixture (RM). A 32percent by weight sodium hydroxide solution is added dropwise to the reaction mixture (RM) to give a pH-value in the range of from 9 to 10. The mixture is heated to a temperature in the range of from 60 to 65° C. and according to step d) separated into a first phase and a second phase. The first phase is cooled to a temperature in the range of from 20 to 30° C. A 31percent by weight hydrochloric acid solution is added dropwise to the first phase to give a pH-value in the range of from 3 to 4. Crystals of 1,2-benzisothiazolin-3one precipitate. The precipitated crystals are collected by filtration, washed with water, and dried to obtain 1,2-benzisothiazolin-3-one (I) (102 g, HPLC>99percent), the yield to 2-chlorobenzonitrile (II) is 93.5percent.The second phase (420 g) is distilled to obtain 1-chlorooctadecane (V) (210 g). 210 g of the 1-chlorooctadecane (V), 200 g of chlorobenzene, 180 g of a 32percent by weight sodium bisulfide solution in water and 6 g of tetra-butylammonium bromide are added into a 1000 ml four-necked flask with a stirrer, a thermometer and a condenser. At a temperature in the range of from 65 to 70° C., the mixture is reacted for 16 h. The mixture is separated into an aqueous layer and an organic layer. The organic layer is n-octadecanethiol (III) (405 g).

Stage 1: With water, chlorine in chlorobenzene, Time= 3h, T= 20 - 65 °C Stage 2: With sodium hydroxide in water, T= 60 - 65 °C , pH= 9 - 10 Stage 3: With hydrochlorid acid in water, T= 20 - 30 °C , pH= 3 - 4 Patent; Shouguang Syntech Fine Chemical Co., Ltd.; DAI, Mingben; US2015/336910; (2015); (A1) English View in Reaxys N

S

Cl

S NH

Cl

N

O

Rx-ID: 41483110 View in Reaxys 23/99 Yield

Conditions & References

106 g, 97.2 5.b; 5.c; 5.d : Example 5 %, 143 g According to step b) 320g of the organic layer, comprising the 2-(dodecylthio)benzonitrile (IV) obtained in step a), 200 g of chlorobenzene and 30 g of water are added into a 1000 ml four-necked flask with a stirrer, a thermometer and a condenser. At a temperature in the range of from 20 to 30° C., 100 g sulfuryl chloride are added dropwise to the mixture over a period of 2 hours. The mixture is further heated to a temperature in the range of from 60 to 65° C. and then allowed to further react for 1 h. During the reaction the reaction mixture (RM) is formed. After completion of the reaction the reaction mixture (RM) is cooled to a temperature in the range of from 20 to 30° C. and according to step c) 200 g of water are added to the reaction mixture (RM). A 32percent by weight sodium hydroxide solution is

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

22/41

2017-09-30 14:38:13

added dropwise to the reaction mixture (RM) to give a pH-value in the range of from 9 to 10. The mixture is heated to a temperature in the range of from 60 to 65° C. and according to step d) separated into a first phase and a second phase. The first phase is cooled to a temperature in the range of from 20 to 30° C. A 31percent by weight hydrochloric acid solution is added dropwise to the first phase to give a pH-value in the range of from 3 to 4. Crystals of 1,2-benzisothiazolin-3-one (I) precipitate. The precipitated crystals are collected by filtration, washed with water, and dried to obtain 1,2-benzisothiazolin-3-one (I) (106 g, HPLC>99percent), the yield to 2-chlorobenzonitrile (II) is 97.2percent. (0277) The second phase (445 g) is distilled to obtain n-chlorododecane (V) (143 g). 143 g of the nchlorododecane (V), 100 g of chlorobenzene, 180 g of a 32percent by weight sodium bisulfide solution in water and 4 g of tetra-butylammonium bromide are added into a 1000 ml four-necked flask with a stirrer, a thermometer and a condenser. At a temperature in the range of from 65 to 70° C., the mixture is reacted for 12 h. The mixture is separated into an aqueous layer and an organic layer. The organic layer is n-dodecanethiol (III) (244 g).

Stage 1: With sulfuryl chloride, water in chlorobenzene, Time= 3h, T= 20 - 65 °C Stage 2: With sodium hydroxide in water, T= 60 - 65 °C , pH= 9 - 10 Stage 3: With hydrochlorid acid in water, T= 20 - 30 °C , pH= 3 - 4, Reagent/catalyst Patent; Shouguang Syntech Fine Chemical Co., Ltd.; DAI, Mingben; US2015/336910; (2015); (A1) English View in Reaxys N

S

Cl

S NH

Cl

N

O

Rx-ID: 41483117 View in Reaxys 24/99 Yield

Conditions & References

103 g, 94.5 2.b; 2.c; 2.d : Example 2 %, 100 g According to step b) 279 g of the organic layer, comprising the 2-(octylthio)benzonitrile (IV) obtained in step a), 200 g of chlorobenzene and 32 g of water are added into a 1000 ml four-necked flask with a stirrer, a thermometer and a condenser. At a temperature in the range of from 20 to 30° C., 54 g chlorine are blown into the mixture over a period of 2 hours. The mixture is further heated to a temperature in the range of from 60 to 65° C. and then allowed to further react for 1 h. During the reaction the reaction mixture (RM) is formed. After completion of the reaction the reaction mixture (RM) is cooled to a temperature in the range of from 20 to 30° C. and according to step c) 200 g of water are added to the reaction mixture (RM). A 32percent by weight sodium hydroxide solution is added dropwise to the reaction mixture (RM) to give a pH-value in the range of from 9 to 10. The mixture is heated to a temperature in the range of from 60 to 65° C. and according to step d) separated into a first phase and a second phase. The first phase is cooled to a temperature in the range of from 20 to 30° C. A 31percent by weight hydrochloric acid solution is added dropwise to the first phase to give a pH-value in the range of from 3 to 4. Crystals of 1,2-benzisothiazolin-3one (I) precipitate. The precipitated crystals are collected by filtration, washed with water, and dried to obtain 1,2benzisothiazolin-3-one (I) (103 g, HPLC>99percent), the yield to 2-chlorobenzonitrile (II) is 94.5percent. (0267) The second phase (310 g) is distilled to obtain 1-chlorooctane (V) (100 g). 100 g of the 1-chlorooctadecane (V), 200 g of chlorobenzene, 167 g of a 32percent by weight sodium bisulfide solution in water and 4 g of tetra-butylammonium bromide are added into a 1000 ml four-necked flask with a stirrer, a thermometer and a condenser. At a temperature in the range of from 65 to 70° C., the mixture is reacted for 12 h. The mixture is separated into an aqueous layer and an organic layer. The organic layer is n-octanethiol (Ill) (196 g).

Stage 1: With water, chlorine in chlorobenzene, Time= 3h, T= 20 - 65 °C Stage 2: With sodium hydroxide in water, T= 60 - 65 °C , pH= 9 - 10 Stage 3: With hydrochlorid acid in water, T= 20 - 30 °C , pH= 3 - 4 Patent; Shouguang Syntech Fine Chemical Co., Ltd.; DAI, Mingben; US2015/336910; (2015); (A1) English View in Reaxys Cl

Cl

Cl H 2N

N

HO

O

Rx-ID: 36867756 View in Reaxys 25/99

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

23/41

2017-09-30 14:38:13

Yield

Conditions & References

43 %, 10 %

With tert.-butylhydroperoxide, tetraethylammonium iodide, ammonium hydrogen carbonate in 1,2-dichloro-ethane, Time= 22h, T= 70 °C Wang, Gao; Yu, Qing-Ying; Chen, Shan-Yong; Yu, Xiao-Qi; Organic and Biomolecular Chemistry; vol. 12; nb. 3; (2014); p. 414 - 417 View in Reaxys

Cl

Cl N

HN

Rx-ID: 37685363 View in Reaxys 26/99 Yield

Conditions & References Reaction Steps: 2 1: iodine / water / 20 °C / |Green chemistry 2: ammonia / water / 20 °C / |Green chemistry With ammonia, iodine in water Yadav, Arvind K.; Srivastava, Vishnu P.; Yadav, Lal Dhar S.; Synthetic Communications; vol. 44; nb. 3; (2014); p.

408 - 416 View in Reaxys

N

I

Cl N

Cl

Rx-ID: 37685441 View in Reaxys 27/99 Yield

Conditions & References General Procedure for the One-Pot Synthesis of Primary Thioamides 3 General procedure: A mixture of aldehyde 1 (1.5 mmol) and iodine (1.6 mmol) in ammonia water (10 mL of 28percent solution) was stirred at room temperature for 30 min. The dark reaction mixture fainted in colour at the end of reaction. The excess of ammonia was removed by stirring at 90 °C. Then, O,O-diethyl dithiophosphoric acid (2) (1.5 mmol) was added and the reaction mixture was stirred at 90 °C for 2-4 h (Table 2). After completion of the reaction (monitored by TLC), the mixture was cooled to r.t. The product thus precipitated was filtered, washed with aqueous sodium thiosulfate solution followed by water and dried under reduced pressure to give pure primary thioamides 3 (Table 2).

With ammonia in water, T= 20 °C , Green chemistry Yadav, Arvind K.; Srivastava, Vishnu P.; Yadav, Lal Dhar S.; Synthetic Communications; vol. 44; nb. 3; (2014); p.

408 - 416 View in Reaxys Cl

Cl

HO

N

O

Rx-ID: 37873191 View in Reaxys 28/99 Yield 93 %

Conditions & References With oxygen, cupric trifluoroacetate, urea in dimethyl sulfoxide, Time= 26h, T= 110 °C , Green chemistry Feng, Qiang; Song, Qiuling; Advanced Synthesis and Catalysis; vol. 356; nb. 8; (2014); p. 1697 - 1702 View in Reaxys

H 2N N

Cl N

Rx-ID: 29687998 View in Reaxys 29/99

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

24/41

2017-09-30 14:38:13

Yield

Conditions & References

63 %

3.4.4 Diazotization–halogenation to aryl chlorides 7 arenediazonium camphorsulfonate General procedure: Camphorsulfonic acid (3.0 mmol), tert-butyl nitrite (3.0 mmol), benzyltriethylammonium chloride (5.0 mmol), and catalytic amounts of copper chloride (1 mol percent) were added to an acetonitrile solution (30 ml) of aniline (2.5 mmol). The reaction mixture was stirred at 60 °C for 24 h (Tables 1 and 2). The evolution of N2 was immediately observed. The solvent was removed by rotary evaporator after completion of the reaction (confirmed by β-naphthol test and TLC). The crude residue was purified via column chromatography by using hexane/dichloromethane as the eluting solvent. Physical and 1H NMR data were identical to those of a commercially available sample of analytical purity.

With N-benzyl-N,N,N-triethylammonium chloride, copper dichloride, CSA, sodium nitrite in acetic acid, Time= 24h, T= 20 °C , Time, Solvent Vajpayee, Vaishali; Moon, Mi Eun; Lee, Sunmi; Ravikumar, Sambandam; Kim, Hyunuk; Ahn, Byungchan; Choi, Seoyoon; Hong, Soon Ho; Chi, Ki-Whan; Tetrahedron; vol. 69; nb. 16; (2013); p. 3511 - 3517 View in Reaxys

61 %

With tert.-butylnitrite, N-benzyl-N,N,N-triethylammonium chloride, toluene-4-sulfonic acid, copper dichloride in acetonitrile, Time= 24h, T= 20 °C Lee, Young Min; Moon, Mi Eun; Vajpayee, Vaishali; Filimonov, Victor D.; Chi, Ki-Whan; Tetrahedron; vol. 66; nb. 37; (2010); p. 7418 - 7422 View in Reaxys

33 %

With tert.-butylnitrite, N-benzyl-N,N,N-triethylammonium chloride, toluene-4-sulfonic acid, copper dichloride Moon, Mi Eun; Choi, Younghwa; Lee, Young Min; Vajpayee, Vaishali; Trusova, Marina; Filimonov, Victor D.; Chi, Ki-Whan; Tetrahedron Letters; vol. 51; nb. 51; (2010); p. 6769 - 6771 View in Reaxys Cl

Cl N

O

Rx-ID: 31423989 View in Reaxys 30/99 Yield 91 %

Conditions & References General procedure for oxidative fragmentation of oxiranes.

General procedure: To a stirred solution of IBX (10.0 mmol) in aqueous ammonia (25 mL of a 28-30percent solution) was added oxirane (5.0 mmol) in 5 mL of acetonitrile in one portion. The reaction mixture was stirred at 70 °C until complete consumption of starting material as observed on TLC (up to 4 h). After completion of reaction, the reaction mixture was extracted with chloroform (2 .x. 15 mL). The organic layer was washed with water (2 .x. 10 mL); bisulfate solution (15 mL) followed by water (10 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give crude product. Pure product was obtained after column chromatography (silica gel, mesh size 60-120, eluent ethyl acetate/hexane 05:95).

With ammonia, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in water, acetonitrile, T= 70 °C Deshmukh, Swapnil S.; Huddar, Sameerana N.; Jadhav, Ravindra R.; Akamanchi, Krishnacharya G.; Tetrahedron Letters; vol. 52; nb. 35; (2011); p. 4533 - 4536 View in Reaxys

83 %

With ammonia, iodine in water, acetonitrile, T= 70 °C Jadhav, Ravindra R.; Akamanchi, Krishnacharya G.; Chemistry Letters; vol. 42; nb. 2; (2013); p. 162 - 164 View in Reaxys Cl

N

N

Rx-ID: 35155084 View in Reaxys 31/99

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

25/41

2017-09-30 14:38:13

Yield

Conditions & References

90 %

With N-chloro-succinimide, palladium diacetate, toluene-4-sulfonic acid in 1,2-dichloro-ethane, Time= 12h, T= 70 °C , Sealed tube Du, Bingnan; Jiang, Xiaoqing; Sun, Peipei; Journal of Organic Chemistry; vol. 78; nb. 6; (2013); p. 2786 - 2791 View in Reaxys

Cl

Cl

Cl H 2N

N O

O

Rx-ID: 35229051 View in Reaxys 32/99 Yield

Conditions & References

87 %

With [Ru(η6-C6Me6)Cl2(tris(dimethylamino)phosphine)], hydroxylamine hydrochloride, sodium hydrogencarbonate in water, Time= 7h, T= 100 °C , Inert atmosphere, Sealed tube, Green chemistry Garcia-Alvarez, Rocio; Diaz-Alvarez, Alba E.; Crochet, Pascale; Cadierno, Victorio; RSC Advances; vol. 3; nb.

17; (2013); p. 5889 - 5894 View in Reaxys

Cl

Cl

Cl HO

Cl H 2N

N

N O

O

Rx-ID: 35258461 View in Reaxys 33/99 Yield

Conditions & References With 4H2O*6K(1+)*PW9V3O40 (6-), ammonia, water, dihydrogen peroxide in isopropyl alcohol, Time= 10h, T= 25 °C Xue, Xiaoling; Song, Fangyuan; Ma, Baochun; Yu, Yongze; Li, Cheng; Ding, Yong; Catalysis Communications; vol. 33; (2013); p. 61 - 65 View in Reaxys N

N (v6)

Fe 4N

N3 H N

N 4

O

H

Cl

Cl

N Br

K+

Rx-ID: 32300638 View in Reaxys 34/99 Yield 82 %

Conditions & References General procedure for cyanation reaction of aryl halides with K4[Fe(CN)6] under microwave irradiation General procedure: A mixture of the aryl halide (1 mmol), K4[Fe(CN)6]*3 H2O (0.22 mmol, 92.9 mg), TBAB (1 mmol, 322.4 mg), palladacycle catalyst (0.5 mmol percent, 4.7 mg), and K2CO3 (1 mmol, 138.2 mg) was added to DMF (3 mL) in a round-bottomed flask equipped with a condenser and placed into the Milestone microwave. Initially using a microwave power of 600 W the temperature was ramped from room temperature to 130 °C, this taking approximately 1 min, and then held at this temperature until the reaction was completed. During this time, the power was modulated automatically to keep the reaction mixture at 130 °C. The mixture was stirred continuously using an appropriate magnet during the reaction. After the reaction was completed, the mixture was cooled to room temperature and diluted with water (30 ml) and ethyl acetate (30 ml). The organic layer was dried over MgSO4, filtered, and the solvent was evaporated using rotary evaporator. The residue was purified by silica gel column chromatography or by recrystallization using ethanol and water. The products were characterized by comparing their mp, IR, 1H, 13C NMR spectra with those found in the literature. [19] and [20] With [Pd{C6H4(CH2N(CH2Ph)2)}(μ-Br)]2, tetrabutylammomium bromide, potassium carbonate in N,N-dimethyl-formamide, Time= 0.166667h, T= 130 °C , Microwave irradiation, chemoselective reaction Hajipour, Abdol Reza; Rafiee, Fatemeh; Ruoho, Arnold E.; Tetrahedron Letters; vol. 53; nb. 5; (2012); p. 526 529 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

26/41

2017-09-30 14:38:13

Cl

Cl

O

P

O

P

N

P

O P

O

Rx-ID: 32545805 View in Reaxys 35/99 Yield

Conditions & References

20 %

With triethylamine in dichloromethane, Time= 0.333333h, T= 20 °C Moussa, Ziad; Synthesis; vol. 44; nb. 3; (2012); p. 460 - 468; Art.No: T105811SS View in Reaxys 4

+ -4K

N

Cl

N

Cl

N (v6)

N

Br

N

Fe N N

Rx-ID: 33236828 View in Reaxys 36/99 Yield

Conditions & References

68 %

With [Pd{C6H3(CH2CH2NH2)-4-OMe-5-κ2-C,N}(μ-Br)]2, potassium carbonate in N,N-dimethyl-formamide, Time= 0.25h, T= 130 °C , Microwave irradiation, chemoselective reaction Hajipour, Abdol-Reza; Abrisham, Fatemeh; Tavakoli, Ghazal; Transition Metal Chemistry; vol. 36; nb. 7; (2011); p. 725 - 730 View in Reaxys Cl

N

Br

N Cl

Rx-ID: 29174726 View in Reaxys 37/99 Yield

Conditions & References

75 %

With 0.60mol Pd/C, hydrogen, sodium hydrogencarbonate in methanol, Time= 0.75h, T= 20 °C , regioselective reaction Ramanathan, Ahalya; Jimenez, Leslie S.; Synthesis; nb. 2; (2010); p. 217 - 220; Art.No: M04609SS View in Reaxys Cl

Cl

H 2N

Cl H 2N

N

HO

O

N

Rx-ID: 29622620 View in Reaxys 38/99 Yield 84 %, 10 %

Conditions & References With tetraethylammonium bromide, 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in acetonitrile, Time= 0.75h, T= 20 °C Deshmukh, Swapnil S.; Huddar, Sameerana N.; Bhalerao, Dinesh S.; Akamanchi, Krishnacharya G.; Arkivoc; vol. 2010; nb. 2; (2010); p. 118 - 126 View in Reaxys

81 %, 8 %

With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione in water, acetonitrile, Time= 0.75h, T= 20 °C Deshmukh, Swapnil S.; Huddar, Sameerana N.; Bhalerao, Dinesh S.; Akamanchi, Krishnacharya G.; Arkivoc; vol. 2010; nb. 2; (2010); p. 118 - 126 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

27/41

2017-09-30 14:38:13

Cl

Cl

Cl

N

O

S

Cl

S

S

Z

N

S

NH

O

NH 2

O

O

Rx-ID: 29760043 View in Reaxys 39/99 Yield

Conditions & References

38 With lithium diisopropyl amide in tetrahydrofuran, hexane, T= -98 °C , Inert atmosphere %Spectr., Vitale, Paola; Di Nunno, Leonardo; Scilimati, Antonio; Synthesis; nb. 18; (2010); p. 3195 - 3203 29 View in Reaxys %Spectr., 23 %Spectr., 6 %Spectr.

Cl

Cl

O N

HO

Rx-ID: 29893160 View in Reaxys 40/99 Yield

Conditions & References

90 %

With hydroxylammonium sulphate, zinc, Time= 0.416667h, Microwave irradiation Cao, Yu-Qing; Qu, An-Li; Liu, Rui-Yan; Duan, Chun-Ming; Journal of Chemical Research; nb. 7; (2010); p. 414 415 View in Reaxys Cl

Cl

Cl

N H 2N

O

Rx-ID: 28945776 View in Reaxys 41/99 Yield

Conditions & References

50 %

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 4 N

K+ -4

F

N

(v6)

Fe N N OC-6

N

Cl

F

F

S O

Cl

O O

N

N

Rx-ID: 28167332 View in Reaxys 42/99 Yield 68 %Chromat.

Conditions & References With 1,1'-bis-(diphenylphosphino)ferrocene, palladium diacetate, sodium carbonate in N,N-dimethyl acetamide, Time= 24h, T= 140 °C , Inert atmosphere Zhu, Yi-Zhong; Cai, Chun; Synthetic Communications; vol. 38; nb. 16; (2008); p. 2753 - 2760 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

28/41

2017-09-30 14:38:13

Cl

Cl NH

N

Li+

N

H

O

Cl

N–

HN

N

O

Cl

H

O

N

racemate

Rx-ID: 28231824 View in Reaxys 43/99 Yield

Conditions & References

40 %, 30 %, 21 %

in tetrahydrofuran, hexanes, Time= 1h, T= 0 °C , Inert atmosphere Di Nunno, Leonardo; Vitale, Paola; Scilimati, Antonio; Tetrahedron; vol. 64; nb. 49; (2008); p. 11198 - 11204 View in Reaxys Cl

Cl

E N

N

N

Rx-ID: 11109773 View in Reaxys 44/99 Yield

Conditions & References With ammonium hydroxide, 1,3-Diiodo-5,5-dimethyl-2,4-imidazolidinedione, Time= 3h, T= 60 °C Iida, Shinpei; Togo, Hideo; Tetrahedron; vol. 63; nb. 34; (2007); p. 8274 - 8281 View in Reaxys Cl E

O

Cl

O

N

N

N

N

O

N O

Rx-ID: 11109775 View in Reaxys 45/99 Yield

Conditions & References With ammonium hydroxide, 1,3-Diiodo-5,5-dimethyl-2,4-imidazolidinedione, Time= 4h, T= 60 °C Iida, Shinpei; Togo, Hideo; Tetrahedron; vol. 63; nb. 34; (2007); p. 8274 - 8281 View in Reaxys Cl

Cl

Cl

H 2N

N H 2N

O

Rx-ID: 9536149 View in Reaxys 46/99 Yield 32 % Chromat., 23 % Chromat.

36 % Chromat., 1.5 % Chromat.

14 % Chromat.,

Conditions & References With sodium tetrahydroborate, lithium chloride in diethylene glycol dimethyl ether, Time= 3h, T= 162 °C , Title compound not separated from byproducts.

Zhu, Hua-Jie; Lu, Kai-Tao; Sun, Guang-Ri; He, Jin-Bao; Li, Hai-Qing; Pittman Jr., Charles U.; New Journal of Chemistry; vol. 27; nb. 2; (2003); p. 409 - 413 View in Reaxys With lithium aluminium tetrahydride in tetrahydrofuran, Time= 1h, T= 20 - 78 °C , Title compound not separated from byproducts.

Zhu, Hua-Jie; Lu, Kai-Tao; Sun, Guang-Ri; He, Jin-Bao; Li, Hai-Qing; Pittman Jr., Charles U.; New Journal of Chemistry; vol. 27; nb. 2; (2003); p. 409 - 413 View in Reaxys With lithium aluminium tetrahydride in tetrahydrofuran, Time= 1h, T= 78 °C , Title compound not separated from byproducts.

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

29/41

2017-09-30 14:38:13

2 % Chromat.

Zhu, Hua-Jie; Lu, Kai-Tao; Sun, Guang-Ri; He, Jin-Bao; Li, Hai-Qing; Pittman Jr., Charles U.; New Journal of Chemistry; vol. 27; nb. 2; (2003); p. 409 - 413 View in Reaxys

55 % Chromat., 16 % Chromat.

With sodium tetrahydroborate, lithium chloride in diethylene glycol dimethyl ether, Time= 5.5h, T= 162 °C , Title compound not separated from byproducts.

Zhu, Hua-Jie; Lu, Kai-Tao; Sun, Guang-Ri; He, Jin-Bao; Li, Hai-Qing; Pittman Jr., Charles U.; New Journal of Chemistry; vol. 27; nb. 2; (2003); p. 409 - 413 View in Reaxys

77 % Chromat., 4 % Chromat.

With sodium tetrahydroborate in diethylene glycol dimethyl ether, Time= 2.6h, T= 162 °C , Title compound not separated from byproducts.

Zhu, Hua-Jie; Lu, Kai-Tao; Sun, Guang-Ri; He, Jin-Bao; Li, Hai-Qing; Pittman Jr., Charles U.; New Journal of Chemistry; vol. 27; nb. 2; (2003); p. 409 - 413 View in Reaxys

O

Cl

Cl

Cl N H

N

N

Rx-ID: 9072577 View in Reaxys 47/99 Yield

Conditions & References With trichlorophosphate in acetonitrile, Time= 3h, Heating Janin, Yves L.; Roulland, Emmanuel; Beurdeley-Thomas, Arnaud; Decaudin, Didier; Monneret, Claude; Poupon, Marie-France; Journal of the Chemical Society. Perkin Transactions 1; nb. 4; (2002); p. 529 - 532 View in Reaxys Cl O

N

Cl

E N

N

Rx-ID: 9275506 View in Reaxys 48/99 Yield 86 %

Conditions & References With zirconium tetrachloride in nitromethane, Time= 0.0333333h, Heating Tsuji, Chiho; Miyazawa, Etsuko; Sakamoto, Takeshi; Kikugawa, Yasuo; Synthetic Communications; vol. 32; nb.

24; (2002); p. 3871 - 3879 View in Reaxys Cl

O H 2N

N

N

Rx-ID: 14441182 View in Reaxys 49/99 Yield

Conditions & References Reaction Steps: 2 1: acetonitrile; H2O / 0.17 h 2: 86 percent / ZrCl4 / nitromethane / 0.03 h / Heating With zirconium tetrachloride in nitromethane, water, acetonitrile Tsuji, Chiho; Miyazawa, Etsuko; Sakamoto, Takeshi; Kikugawa, Yasuo; Synthetic Communications; vol. 32; nb.

24; (2002); p. 3871 - 3879 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

30/41

2017-09-30 14:38:13

Cl

Cl

O

salicylic acid chloride ; 2-chloro-trichloromethyl-benzene

N

Cl

Rx-ID: 14737467 View in Reaxys 50/99 Yield

Conditions & References Reaction Steps: 2 1: triethylamine / acetonitrile / 2 h 2: POCl3 / acetonitrile / 3 h / Heating With triethylamine, trichlorophosphate in acetonitrile Janin, Yves L.; Roulland, Emmanuel; Beurdeley-Thomas, Arnaud; Decaudin, Didier; Monneret, Claude; Poupon, Marie-France; Journal of the Chemical Society. Perkin Transactions 1; nb. 4; (2002); p. 529 - 532 View in Reaxys Cl

Cl

N

N H 2N

Rx-ID: 8878782 View in Reaxys 51/99 Yield

Conditions & References

82 %

With sodium hydrogensulfite, sodium nitrite in ethanol, water, acetic acid, Time= 4h, T= 24 °C Geoffroy, Otto J.; Morinelli, Thomas A.; Meier, G. Patrick; Tetrahedron Letters; vol. 42; nb. 32; (2001); p. 5367 5369 View in Reaxys Cl

N

Cl

N

N

Rx-ID: 8681260 View in Reaxys 52/99 Yield

Conditions & References

84 %

With aluminum oxide, Oxonereg;, Time= 0.1h, microwave irradiation Ramalingam; Subba Reddy; Srinivas; Yadav; Synthetic Communications; vol. 30; nb. 24; (2000); p. 4507 - 4512 View in Reaxys Cl

H N

O

N

Cl

E N

O

Rx-ID: 5294602 View in Reaxys 53/99 Yield

Conditions & References

93 %

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

H 2N

H N

O O

Cl

O O

S

2-chloro-benzaldehyde seqtrans-oxime

N

HO

Rx-ID: 16146157 View in Reaxys 54/99 Yield

Conditions & References Reaction Steps: 2 1: 95 percent / ethanol / 1 h / 20 °C 2: 93 percent / TsOH*H2O / toluene / 0.5 h / Heating With toluene-4-sulfonic acid in ethanol, toluene, 1: Condensation / 2: Elimination

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

31/41

2017-09-30 14:38:13

Coskun, Necdet; Arikan, Nevin; Tetrahedron; vol. 55; nb. 40; (1999); p. 11943 - 11948 View in Reaxys N

Cl N

Rx-ID: 24679388 View in Reaxys 55/99 Yield

Conditions & References 47 : Cross-coupling of 2-chlorobenzonitrile with 4-tolueneboronic acid Example 47 Cross-coupling of 2-chlorobenzonitrile with 4-tolueneboronic acid To prepare the catalyst, 38.8 mg (0.219 mmol) of palladium(II) chloride and 54.0 mg (0.657 mmol) of sodium acetate are stirred for 30 minutes at 23° C. in 2.4 ml of DMSO under an argon atmosphere.

Subsequently, 1.99 ml (0.875 mmol) of a 0.44 molar aqueous solution of sodium 4-diphenylphosphinophenylphosphinate, prepared as described below, are added and the suspension is stirred for a further 30 minutes at 23° C. Under an argon atmosphere, 30.0 g (0.2181 mol) of 2-chlorobenzonitrile, 32.6 g (0.240 mol) of 4-tolueneboronic acid and 16.2 g (70 mol percent) of sodium carbonate are stirred into 120 ml of ethylene glycol.

20 ml of water are added and the mixture is heated to 80° C. The above-described catalyst suspension is then added and the mixture is heated for 5 hours under reflux.

At 23° C., the mixture is admixed with 100 ml of ethyl acetate.

The organic phase is separated off, evaporated on a rotary evaporator and fractionally distilled under reduced pressure.

This gives 31.6 g (75percent of theory) of 2-cyano-4'-methylbiphenyl (bp. 140° C./1.0 mbar; mp. 50° C.).

Patent; Hoechst Aktiengesellschaft; US5756804; (1998); (A1) English View in Reaxys Cl

HO

N

Cl

Cl

Cl

E

N

O N

N

O

N

HO

Rx-ID: 4739457 View in Reaxys 56/99 Yield

Conditions & References

17 %, 6 % Chromat., 47 %

With ammonium cerium(IV) nitrate, Time= 1h, T= 70 °C Giurg; Mlochowski; Polish Journal of Chemistry; vol. 71; nb. 8; (1997); p. 1093 - 1101 View in Reaxys

Cl N

Cl

Cl Cl

N

N

Cl

N

N

Cl Cl

Cl

Rx-ID: 2041854 View in Reaxys 57/99 Yield

Conditions & References With (C2H5)3NH2CO2, palladium on activated charcoal in acetonitrile, T= 80 °C , Yield given Pews; Hunter; Wehrmeyer; Tetrahedron; vol. 49; nb. 22; (1993); p. 4809 - 4820 View in Reaxys

Cl N

S

Cl

Cl O

S

S8

S

N

O

S

O

N

Rx-ID: 8427951 View in Reaxys 58/99 Yield 38 %

Conditions & References in xylene, Time= 5h, Heating

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

32/41

2017-09-30 14:38:13

Wai, Kwok-Fai; Sammes, Michael P.; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 1; (1991); p. 183 - 187 View in Reaxys

Cl

Cl

S

N S

N

N

S

S Cl

O

O

S8

O

Rx-ID: 8427965 View in Reaxys 59/99 Yield

Conditions & References

25 %

in xylene, Time= 4h, Heating Wai, Kwok-Fai; Sammes, Michael P.; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 1; (1991); p. 183 - 187 View in Reaxys Br

Cl

N

N

Rx-ID: 3962056 View in Reaxys 60/99 Yield

Conditions & References

93 % Chromat.

With CuCl-alumina in various solvent(s), Time= 6h, T= 150 °C Clark, James H.; Jones, Craig W.; Duke, Catherine V. A.; Miller, Jack M.; Journal of Chemical Research, Miniprint; nb. 8; (1989); p. 1745 - 1758 View in Reaxys Cl

N

(η6-chlorobenzene)(η5-cyclopentadienyl)iron hexafluorophosphate

Na

N

Rx-ID: 6520244 View in Reaxys 61/99 Yield

Conditions & References With 2,3-dicyano-5,6-dichloro-p-benzoquinone, 1.) DMF, r.t., 3 min; 2.) CH3CN, r.t., Yield given. Multistep reaction Sutherland, Ronald G.; Zhang, Chun-Hao; Piorko, Adam; Lee, Choi Chuck; Canadian Journal of Chemistry; vol.

67; (1989); p. 137 - 142 View in Reaxys

Cl

Cl N

K

N

N Cl

N

Rx-ID: 3394699 View in Reaxys 62/99 Yield

Conditions & References With NiBr2(PPh3)2 in N,N,N',N',N'',N''-hexamethylphosphoric triamide, Time= 16h, T= 60 °C Sakakibara, Yasumasa; Okuda, Fumio; Shimobayashi, Akira; Kirini, Kunihiko; Sakai, Mutsuji; et al.; Bulletin of the Chemical Society of Japan; vol. 61; (1988); p. 1985 - 1990 View in Reaxys Cl

Cl H 2N

N S

Rx-ID: 2958489 View in Reaxys 63/99

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

33/41

2017-09-30 14:38:13

Yield

Conditions & References

98 %

With polystyrene-bound diaryl telluroxide in dichloromethane, Time= 1h, Ambient temperature Hu, Nan Xing; Aso, Yoshio; Otsubo, Tetsuo; Ogura, Fumio; Bulletin of the Chemical Society of Japan; vol. 59; nb. 3; (1986); p. 879 - 884 View in Reaxys

95 %

With polystyrne-bound selenoxide in ethanol, Time= 24h, Heating Hu, Nan Xing; Aso, Yoshio; Otsubo, Tetsuo; Ogura, Fumio; Chemistry Letters; (1985); p. 603 - 606 View in Reaxys Cl

HO

Cl N

Cl

Cl

Cl

Cl

N

O

Rx-ID: 3795546 View in Reaxys 64/99 Yield

Conditions & References

88 %

With triethylamine in dichloromethane, Time= 1h, Ambient temperature Saednya, Akbar; Synthesis; nb. 9; (1983); p. 748 - 749 View in Reaxys

S

N Cl

H N

O O

N

Cl

N

N

NH 2

N

O

O Cl

O

N

N

O

S

N

N

N

S

Rx-ID: 2603352 View in Reaxys 65/99 Yield

Conditions & References

27.0 %, 21.7 %

in pyridine, Time= 1h, Heating, other temp. and time, Product distribution, Mechanism Yamazaki, Chiji; Journal of Organic Chemistry; vol. 46; nb. 20; (1981); p. 3956 - 3959 View in Reaxys Cl

N

N

N

Cl

Cl

Cl

N

N

N

Rx-ID: 3377264 View in Reaxys 66/99 Yield

Conditions & References gaseous plasma of glow discharge, Yield given. Further byproducts given. Yields of byproduct given So, Y. H.; Miller, Larry L.; Journal of the American Chemical Society; vol. 103; nb. 14; (1981); p. 4204 - 4209 View in Reaxys

N

N

Cl

Cl N

Cl

N

Cl N

N

N

Rx-ID: 3377265 View in Reaxys 67/99 Yield 17 % Chromat., 19 % Chromat.,

Conditions & References plasma apparatus; a variety of substituted benzenes and pyridine similarly cyanated, Product distribution So, Ying-Hung; Miller, Larry L.; Journal of the American Chemical Society; vol. 102; nb. 23; (1980); p. 7119 - 7120 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

34/41

2017-09-30 14:38:13

17 % Chromat., 20 % Chromat.

Cl

H 2N N

Cl

Rx-ID: 721001 View in Reaxys 68/99 Yield

Conditions & References With sulfuric acid, sodium nitrite, Eintragen der erhaltenen Diazoniumsalz-Loesung in eine aus Natriumcyanid und Kupfer(I)-cyanid in Wasser bereitete Loesung bei 70-80grad Hodgson; Heyworth; Journal of the Chemical Society; (1949); p. 1131 View in Reaxys With sulfuric acid, sodium nitrite, Eintragen der erhaltenen Diazoniumsalz-Loesung in eine aus Kaliumcyanid und Kupfer(I)-cyanid in Wasser bereitete Loesung bei 30-40grad Hodgson; Heyworth; Journal of the Chemical Society; (1949); p. 1131 View in Reaxys Diazotization.Behandlung der Diazoloesung mit Kaliumkupfercyanuerloesung Montagne; Recueil des Travaux Chimiques des Pays-Bas; vol. 19; (1900); p. 55 View in Reaxys N

Cl

Cl

copper

N

N

Cl

N

Rx-ID: 6076175 View in Reaxys 69/99 Yield

Conditions & References T= 700 - 750 °C Patent; Farbenfabr. Bayer; DE842045; (1948); View in Reaxys T= 800 °C Patent; Farbenfabr. Bayer; DE842045; (1948); View in Reaxys Cl

sodium-<2-chloro benzoate>

N

Rx-ID: 6520250 View in Reaxys 70/99 Yield

Conditions & References T= 250 °C , Einleiten von Chlorcyan Zappi; Bouso; Anales de la Asociacion Quimica Argentina (1921-2001); vol. 35; (1947); p. 137; ; (1948); p. 7704 View in Reaxys Cl N

O

Cl

Cl

Cl Br

Mg

N

O

Rx-ID: 171807 View in Reaxys 71/99

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

35/41

2017-09-30 14:38:13

Yield

Conditions & References T= -45 °C Le Maistre; Rainsford; Hauser; Journal of Organic Chemistry; vol. 4; (1939); p. 106,107, 109 View in Reaxys Cl Cl

N Z N

OH

copper

N

N

Rx-ID: 6520247 View in Reaxys 72/99 Yield

Conditions & References Stephenson; Waters; Journal of the Chemical Society; (1939); p. 1796,1802 View in Reaxys

Cl Cl

N Z N

copper

N

Cl

N

Rx-ID: 6674980 View in Reaxys 73/99 Yield

Conditions & References Stephenson; Waters; Journal of the Chemical Society; (1939); p. 1796,1802 View in Reaxys Cl Cl

N Z N

O

copper

Cl

N

N

Rx-ID: 6682791 View in Reaxys 74/99 Yield

Conditions & References Stephenson; Waters; Journal of the Chemical Society; (1939); p. 1796,1802 View in Reaxys Cl O

Cl

N Z N

copper

Cl

N

N

Rx-ID: 6682792 View in Reaxys 75/99 Yield

Conditions & References Stephenson; Waters; Journal of the Chemical Society; (1939); p. 1796,1802 View in Reaxys Cl Cl

Cl

Cl

Cl

Cl

N Z N

copper

Cl

N Cl

N

Rx-ID: 6682914 View in Reaxys 76/99 Yield

Conditions & References Stephenson; Waters; Journal of the Chemical Society; (1939); p. 1796,1802 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

36/41

2017-09-30 14:38:13

Cl

Cl

copper (I)-cyanide

N

Cl

Rx-ID: 6520246 View in Reaxys 77/99 Yield

Conditions & References With quinoline, copper(I) bromide, T= 200 °C Patent; Gen. Aniline and Film Co.; US2195076; (1937) View in Reaxys Cl N

Cl

Cl

Cl

Cl

OH

Cl

Cl N

Rx-ID: 60815 View in Reaxys 78/99 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 Cl O

O

N

O

Cl

N

E

O

O

O

Cl HO

N

Cl

E

O

N

HO

O

Rx-ID: 441645 View in Reaxys 79/99 Yield

Conditions & References Brady; McHugh; Journal of the Chemical Society; vol. 123; (1923); p. 1198 View in Reaxys Hauser; Jordan; O'Connor; Journal of the American Chemical Society; vol. 57; (1935); p. 2456 View in Reaxys

Cl N

Cl

Cl N

Rx-ID: 455230 View in Reaxys 80/99 Yield

Conditions & References With sodium ethanolate Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4517 View in Reaxys With potassium hydroxide Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4517 View in Reaxys T= 275 °C Hauser; Hauser; Journal of the American Chemical Society; vol. 52; (1930); p. 2050,2052 View in Reaxys Hauser; Gillaspie; Le Maistre; Journal of the American Chemical Society; vol. 57; (1935); p. 567 View in Reaxys T= 30 °C , Aufbewahren im Exsiccator ueber NaOH Hauser; Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4158,4161

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

37/41

2017-09-30 14:38:13

View in Reaxys Cl N Cl

Cl

Cl

Cl

Cl

Cl

aqueous dioxane

N

Rx-ID: 7977301 View in Reaxys 81/99 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

Cl N

Cl

Cl

2-chloro-benzaldehyde imine hydrochloride

N

Rx-ID: 7998592 View in Reaxys 82/99 Yield

Conditions & References T= 215 °C , Thermolysis Hauser; Hauser; Journal of the American Chemical Society; vol. 52; (1930); p. 2050,2052 View in Reaxys Hauser; Gillaspie; Le Maistre; Journal of the American Chemical Society; vol. 57; (1935); p. 567 View in Reaxys Hauser; Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4158,4161 View in Reaxys Cl O

O

N

E

aqueous NaOH

O

Cl

Cl

O

2-chloro-benzaldehyde seqtrans-oxime

N

HO

Rx-ID: 8264265 View in Reaxys 83/99 Yield

Conditions & References T= 100 °C Hauser; Jordan; O'Connor; Journal of the American Chemical Society; vol. 57; (1935); p. 2456 View in Reaxys

Cl

Cl N

N

Cl

H

2.2'-dichloro-trans-stilbene

N

Cl

Rx-ID: 7543799 View in Reaxys 84/99 Yield

Conditions & References Bei der Destillation unter Normaldruck Howard et al.; Journal of the American Chemical Society; vol. 54; (1932); p. 3628,3635 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

38/41

2017-09-30 14:38:13

Cl N OH

Cl O– Na +

Cl

N

Rx-ID: 192135 View in Reaxys 85/99 Yield

Conditions & References T= 0 °C Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4517 View in Reaxys Cl N OH

Cl

KO H

Cl

N

Rx-ID: 7977302 View in Reaxys 86/99 Yield

Conditions & References T= 0 °C Hauser; Gillaspie; Journal of the American Chemical Society; vol. 52; (1930); p. 4517 View in Reaxys Cl

Cl Cl

ammonium-<2-chloro benzoate>

N

Cl

Rx-ID: 6520245 View in Reaxys 87/99 Yield

Conditions & References T= 200 - 210 °C Patent; I.G. Farbenind.; DE524715; (1929); Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 18; p. 438 View in Reaxys Cl

N

Cl

potassium-nickel (II)-cyanide

N+

N

Rx-ID: 6520249 View in Reaxys 88/99 Yield

Conditions & References Korczynski; Fandrich; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 183; (1926); p. 422 View in Reaxys Cl

Cl OH

I

H 2N

Ag2O

N

O

Rx-ID: 5802291 View in Reaxys 89/99 Yield

Conditions & References Lander; Jewson; Journal of the Chemical Society; vol. 83; (1903); p. 770 View in Reaxys O

Cl Cl

PCl Cl

O

S

NH

Cl N

Cl

O

Rx-ID: 5436216 View in Reaxys 90/99

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

39/41

2017-09-30 14:38:13

Yield

Conditions & References T= 230 °C Maselli; Gazzetta Chimica Italiana; vol. 30 II; (1900); p. 531 View in Reaxys

Cl

H 2N

potassium cyanocuprate(I)

N

Cl

Rx-ID: 6520248 View in Reaxys 91/99 Yield

Conditions & References With hydrogenchloride, sodium nitrite, die Loesung mit Wasserdampf destillieren Montagne; Recueil des Travaux Chimiques des Pays-Bas; vol. 19; (1900); p. 55 View in Reaxys Cl

Cl

Cl –

N+

N

potassium cyanocuprate(I)

N

Rx-ID: 7977303 View in Reaxys 92/99 Yield

Conditions & References Montagne; Recueil des Travaux Chimiques des Pays-Bas; vol. 19; (1900); p. 55 View in Reaxys Cl

HO

N

Cl

E

N

Rx-ID: 304550 View in Reaxys 93/99 Yield

Conditions & References With acetic anhydride, Einw. von Soda auf die Acetylverbindung Behrend; Nissen; Justus Liebigs Annalen der Chemie; vol. 269; (1892); p. 396 View in Reaxys Cl

N

O

Z

O

Cl

O

N

OH

Rx-ID: 558717 View in Reaxys 94/99 Yield

Conditions & References Behandeln des Reaktionsprodukts mit Alkalien Behrend; Nissen; Justus Liebigs Annalen der Chemie; vol. 269; (1892); p. 396 View in Reaxys

HO N OH

N

Cl

N N

OH

Rx-ID: 495856 View in Reaxys 95/99 Yield

Conditions & References With phosphorus pentachloride

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

40/41

2017-09-30 14:38:13

Henry; Chemische Berichte; vol. 2; (1869); p. 492 View in Reaxys Cl

HO H 2N

N O

Rx-ID: 782949 View in Reaxys 96/99 Yield

Conditions & References With phosphorus pentachloride Henry; Chemische Berichte; vol. 2; (1869); p. 492 View in Reaxys

HO N

Cl

Cl Cl

OH

PCl Cl

N

N N

Cl

OH

Rx-ID: 5436215 View in Reaxys 97/99 Yield

Conditions & References Henry; Chemische Berichte; vol. 2; (1869); p. 492 View in Reaxys

PCl Cl Cl

Cl

HO

Cl Cl

H 2N

N O

Rx-ID: 5802290 View in Reaxys 98/99 Yield

Conditions & References Henry; Chemische Berichte; vol. 2; (1869); p. 492 View in Reaxys Cl

2-chloro-benzoamide

N

Rx-ID: 6520243 View in Reaxys 99/99 Yield

Conditions & References With phosphorus pentachloride Henry; Chemische Berichte; vol. 2; (1869); p. 492 View in Reaxys With tetraphosphorus decasulfide Henry; Chemische Berichte; vol. 2; (1869); p. 492 View in Reaxys

Copyright © 2017 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

41/41

2017-09-30 14:38:13