2-Fluorobenzonitrile by Asch

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41 reactions in Reaxys

2017-09-30 13h:32m:16s (EST)

1. Query

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

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Rx-ID: 1767977 View in Reaxys 1/41 Yield 76 %

Conditions & References With potassium fluoride in various solvent(s), Time= 2h, T= 290 °C , p= 2206.5Torr Suzuki, Hiroshi; Kimura, Yoshikazu; Journal of Fluorine Chemistry; vol. 52; nb. 3; (1991); p. 341 - 351 View in Reaxys With tetrabutyl ammonium fluoride in dimethyl sulfoxide, Time= 18h, T= 20 °C Sun, Haoran; DiMagno, Stephen G.; Angewandte Chemie - International Edition; vol. 45; nb. 17; (2006); p. 2720 2725 View in Reaxys

95.8 With tetrabutyl ammonium fluoride in tetrahydrofuran, Time= 30h, T= 20 °C , Inert atmosphere, chemoselective re%Chromat. action Hu, Yu Feng; Luo, Jun; Lue, Chun Xu; Chinese Chemical Letters; vol. 21; nb. 2; (2010); p. 151 - 154 View in Reaxys 28 %Spectr.

With p-methoxybenzoyl fluoride, 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene in N,N-dimethyl-formamide, Time= 16h, T= 25 °C , Inert atmosphere Ryan, Sarah J.; Schimler, Sydonie D.; Bland, Douglas C.; Sanford, Melanie S.; Organic Letters; vol. 17; nb. 8; (2015); p. 1866 - 1869 View in Reaxys

100 %Spectr.

With tetramethylammonium fluoride in N,N-dimethyl-formamide, Time= 24h, T= 80 °C , Sealed tube, Reagent/catalyst, Temperature, Time Schimler, Sydonie D.; Ryan, Sarah J.; Bland, Douglas C.; Anderson, John E.; Sanford, Melanie S.; Journal of Organic Chemistry; vol. 80; nb. 24; (2015); p. 12137 - 12145 View in Reaxys

94 %Spectr.

The reactions of 3a-e with anhydrous NMe F were compared to those with CsF, a more traditional reagent for SNAT fluorination. At 80 °C, CsF afforded <5percent yield of 4 in all cases. At 140 °C (more typical conditions for CsF halex reactions) (JP 2011 153115 A: WO 2010018857; WO 2009014100: Hyohdoh, I.; et al., ACS Med. Chem. Lett. 2013;4: 1059: Finger, G.C.; et al, J. Am. Chem. Soc. 1956;78:6034), the aryl halides 3a-c reacted with CsF to afford 4 in moderate 22-52percent yield (entries 1-3). In all of these cases, unreacted starting material remained after 24 h at 140 °C. With tetramethylammonium fluoride in N,N-dimethyl-formamide, Time= 3h, T= 80 °C , Temperature, Reagent/catalyst Patent; DOW AGROSCIENCES LLC; THE REGENTS OF THE UNIVERSITY OF MICHIGAN; SANFORD, Melanie; RYAN, Sarah; SCHIMLER, Sydonie; CHENG, Yang; BLAND, Douglas; (47 pag.); WO2017/24167; (2017); (A1) English View in Reaxys

Rx-ID: 3569591 View in Reaxys 2/41 Yield > 95 %

Conditions & References With tetrabutyl ammonium fluoride in tetrahydrofuran, Time= 0.166667h, Inert atmosphere, Microwave irradiation LaBeaume, Paul; Placzek, Michael; Daniels, Mathew; Kendrick, Ian; Ng, Patrick; McNeel, Melissa; Afroze, Roushan; Alexander, Abigail; Thomas, Rhiannon; Kallmerten, Amy E.; Jones, Graham B.; Tetrahedron Letters; vol. 51; nb. 14; (2010); p. 1906 - 1909 View in Reaxys

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100 % Chromat.

With tetramethylammonium fluoride in dimethyl sulfoxide, Time= 1h, T= 80 °C Boechat, Nubia; Clark, James H.; Journal of the Chemical Society, Chemical Communications; nb. 11; (1993); p. 921 - 922 View in Reaxys With tetrabutyl ammonium fluoride in dimethyl sulfoxide, Time= 0.166667h, T= 20 °C Sun, Haoran; DiMagno, Stephen G.; Angewandte Chemie - International Edition; vol. 45; nb. 17; (2006); p. 2720 2725 View in Reaxys

97.3 With tetrabutyl ammonium fluoride in tetrahydrofuran, Time= 1h, T= 20 °C , Inert atmosphere, chemoselective reac%Chromat. tion Hu, Yu Feng; Luo, Jun; Lue, Chun Xu; Chinese Chemical Letters; vol. 21; nb. 2; (2010); p. 151 - 154 View in Reaxys 99 %Spectr.

97 %Spectr.

With tetramethylammonium fluoride in N,N-dimethyl-formamide, Time= 3h, T= 80 °C , Sealed tube, Reagent/catalyst, Temperature Schimler, Sydonie D.; Ryan, Sarah J.; Bland, Douglas C.; Anderson, John E.; Sanford, Melanie S.; Journal of Organic Chemistry; vol. 80; nb. 24; (2015); p. 12137 - 12145 View in Reaxys

97 %Spectr.

F N

Rx-ID: 28592811 View in Reaxys 3/41 Yield 80%

Conditions & References With formic acid, hydroxylamine hydrochloride, Time= 20h, Reflux Xi, Guoqin; Han, Xiuling; Lu, Xiyan; Advanced Synthesis and Catalysis; vol. 354; nb. 14-15; (2012); p. 2701 2705,5 View in Reaxys

77 %

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

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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 68 %

With 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy, ammonium acetate, sodium perchlorate in acetonitrile, T= 20 °C , Electrolysis, Reagent/catalyst Yang, Xianjing; Fan, Zhongquan; Shen, Zhenlu; Li, Meichao; Electrochimica Acta; vol. 226; (2017); p. 53 - 59 View in Reaxys With tert.-butylhydroperoxide, ammonia, potassium iodide in water, Time= 8h, T= 60 °C Rajender Reddy; Uma Maheswari; Venkateshwar; Prashanthi; Lakshmi Kantam; Tetrahedron Letters; vol. 50; nb. 18; (2009); p. 2050 - 2053 View in Reaxys

7 %Chromat.

General procedure for the synthesis of nitriles: A pressure tube was charged with an appropriate amount of Zn(OTf)2 (0.036 mmol, 5.0 mol percent), the corresponding aldehyde (0.72 mmol) and hydroxylamine hydrochloride (1.2 equiv, 0.86 mmol). After the addition of toluene (2.0 mL) the reaction mixture was stirred in a preheated oil bath at 100 °C for 24 h. The mixture was cooled in an ice bath and biphenyl (internal standard) was added. The solution was diluted with dichloromethane and an aliquot was taken for GC-analysis (30 m Rxi-5 ms column, 40-300 °C). The solvent was carefully removed and the residue was purified by column chromatography (n-hexane/ethyl acetate). The analytical properties of the corresponding nitriles are in agreement with the literature. With hydroxylamine hydrochloride, zinc trifluoromethanesulfonate in toluene, Time= 24h, T= 100 °C Enthaler, Stephan; Weidauer, Maik; Schroeder, Fanny; Tetrahedron Letters; vol. 53; nb. 7; (2012); p. 882 - 885 View in Reaxys

100 %Spectr.

With [BMIM(SO3H)][OTf], trimethylsilylazide, 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate, Time= 3h, T= 20 - 50 °C , Sonication, Schmidt Reaction Nandi, Ganesh C.; Laali, Kenneth K.; Tetrahedron Letters; vol. 54; nb. 17; (2013); p. 2177 - 2179 View in Reaxys General procedure for preparation of compounds a1–a17 General procedure: A mixture of aromatic aldehydes (50mmol) (1–17), hydroxylamine hydrochloride (62.5mmol), sodium acetate (125mmol) were dissolved in the mixture of formic acid and water (60:40) and stirred at 80°C until TLC analysis indicated the disappearance of aromatic aldehydes. Then, cooling the reaction system to room temperature and put it into water to obtain the target compounds. Some desired products which were dissolved in the mixture of water and formic acid can be obtained by salting out. Then, solid target compounds were obtained by filtration and recrystallized by alcohol, and then dried under vacuum. While, some target compounds are oily. These oily compounds were obtained by extraction with ethyl acetate and the solvent was removed at the vacuum to afford aryl nitriles (a1–a17). With formic acid, hydroxylamine hydrochloride, sodium acetate in water, T= 80 °C Lin, Hong-Yan; Li, Zi-Kang; Bai, Li-Fei; Baloch, Shahla Karim; Wang, Fang; Qiu, Han-Yue; Wang, Xue; Qi, JinLiang; Yang, Raong-Wu; Wang, Xiao-Ming; Yang, Yong-Hua; Biochemical Pharmacology; vol. 96; nb. 2; (2015); p. 93 - 106 View in Reaxys

Br N

F N

Rx-ID: 41657022 View in Reaxys 4/41

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Yield

Conditions & References

95 %Spectr.

Rx-ID: 41657023 View in Reaxys 5/41 Yield

Conditions & References

88 %Spectr.

S O

O N

Rx-ID: 41657024 View in Reaxys 6/41 Yield 73 %Spectr.

Conditions & References With cesium fluoride in N,N-dimethyl-formamide, Time= 24h, T= 140 °C , Sealed tube, Reagent/catalyst, Temperature

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Schimler, Sydonie D.; Ryan, Sarah J.; Bland, Douglas C.; Anderson, John E.; Sanford, Melanie S.; Journal of Organic Chemistry; vol. 80; nb. 24; (2015); p. 12137 - 12145 View in Reaxys 73 %Spectr.

The reactions of 3a-e with anhydrous NMe F were compared to those with CsF, a more traditional reagent for SNAT fluorination. At 80 °C, CsF afforded <5percent yield of 4 in all cases. At 140 °C (more typical conditions for CsF halex reactions) (JP 2011 153115 A: WO 2010018857; WO 2009014100: Hyohdoh, I.; et al., ACS Med. Chem. Lett. 2013;4: 1059: Finger, G.C.; et al, J. Am. Chem. Soc. 1956;78:6034), the aryl halides 3a-c reacted with CsF to afford 4 in moderate 22-52percent yield (entries 1-3). In all of these cases, unreacted starting material remained after 24 h at 140 °C. With cesium fluoride in N,N-dimethyl-formamide, Time= 24h, T= 140 °C , Temperature, Reagent/catalyst Patent; DOW AGROSCIENCES LLC; THE REGENTS OF THE UNIVERSITY OF MICHIGAN; SANFORD, Melanie; RYAN, Sarah; SCHIMLER, Sydonie; CHENG, Yang; BLAND, Douglas; (47 pag.); WO2017/24167; (2017); (A1) English View in Reaxys

F N

Rx-ID: 44460998 View in Reaxys 7/41 Yield

Conditions & References

87 %

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 F

N H 2N

Rx-ID: 44752133 View in Reaxys 8/41 Yield

Conditions & References

59.2 %

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

O O

O S

N N

Rx-ID: 44761697 View in Reaxys 9/41 Yield 54 %Spectr.

Conditions & References With tetramethylammonium fluoride in N,N-dimethyl-formamide, Time= 24h, T= 80 °C , Inert atmosphere, Glovebox, Sealed tube Schimler, Sydonie D.; Cismesia, Megan A.; Hanley, Patrick S.; Froese, Robert D.J.; Jansma, Matthew J.; Bland, Douglas C.; Sanford, Melanie S.; Journal of the American Chemical Society; vol. 139; nb. 4; (2017); p. 1452 - 1455

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View in Reaxys HO

Rx-ID: 44761709 View in Reaxys 10/41 Yield

Conditions & References Reaction Steps: 2 1: sulphuryl fluoride; potassium carbonate / ethyl acetate / 4 h / 20 °C 2: tetramethylammonium fluoride / N,N-dimethyl-formamide / 24 h / 80 °C / |Inert atmosphere; |Glovebox; |Sealed tube With sulphuryl fluoride, tetramethylammonium fluoride, potassium carbonate in ethyl acetate, N,N-dimethyl-formamide Schimler, Sydonie D.; Cismesia, Megan A.; Hanley, Patrick S.; Froese, Robert D.J.; Jansma, Matthew J.; Bland, Douglas C.; Sanford, Melanie S.; Journal of the American Chemical Society; vol. 139; nb. 4; (2017); p. 1452 - 1455 View in Reaxys F

–C

Zn 2+

N O

Rx-ID: 45539217 View in Reaxys 11/41 Yield

Conditions & References

70 %

With palladium diacetate, cyclohexyldiphenylphosphine in 1,4-dioxane, Time= 16h, T= 150 °C , Inert atmosphere, Schlenk technique, chemoselective reaction Shi, Shicheng; Szostak, Michal; Organic Letters; vol. 19; nb. 12; (2017); p. 3095 - 3098 View in Reaxys

N N

H 2N

Rx-ID: 45552942 View in Reaxys 12/41 Yield

Conditions & References

65 %

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 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 F N

Rx-ID: 7246488 View in Reaxys 13/41 Yield 92%

Conditions & References C.4 : Preparation of 2-fluorobenzonitrile From 2-chlorobenzonitrile COMPARATIVE EXAMPLE 4

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Preparation of 2-fluorobenzonitrile From 2-chlorobenzonitrile The procedure of Example 3 is repeated but without addition of nitrobenzene. Yield: 92percent Selectivity: 94percent Benzonitrile content: 0.35percent Patent; Aventis Research and Technologies GmbH and Co KG; US6166242; (2000); (A1) English View in Reaxys 91 %

5 : Preparation of 2-fluorobenzonitrile From 2-chlorobenzonitrile EXAMPLE 5 Preparation of 2-fluorobenzonitrile From 2-chlorobenzonitrile The procedure of Example 3 is repeated but using 2.5 g of bis(4-nitrophenyl)ether in place of the nitrobenzene. Yield: 91 percent Benzonitrile content: 0.01 percent Patent; Aventis Research and Technologies GmbH and Co KG; US6166242; (2000); (A1) English View in Reaxys

77 %

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 Luecke; Winter; Chimia; vol. 25; (1971); p. 94 View in Reaxys Ishikawa; Inoue; Yuki Gosei Kagaku Kyokaishi; vol. 27; (1969); p. 993,996; ; vol. 72; nb. 21417 View in Reaxys Spagnolo et al.; Journal of the Chemical Society [Section] B: Physical Organic; (1971); p. 2006 View in Reaxys Becke; Burger; Justus Liebigs Annalen der Chemie; vol. 716; (1968); p. 78 View in Reaxys Crow; Wentrup; Tetrahedron Letters; (1968); p. 5569 View in Reaxys 11 Patent; IHARA CHEMICAL INDUSTRY CO., LTD.; EP1555257; (2005); (A1) English View in Reaxys The fluoroaromatic compounds resulting from carrying out the process of this invention using the illustrative chloroaromatic compounds (a) through (z) above are set forth below, followed by utilities for such resulting compounds: (a) 2-fluorobenzonitrile (b) 4-fluorobenzonitrile (c) 2-fluorobenzoyl chloride (d) 4-fluorobenzoyl chloride (e) 2-fluorobenzoyl fluoride ... Patent; Mallinckrodt, Inc.; US4849552; (1989); (A1) English View in Reaxys Again following the same procedure and using in place of benzonitrile an equivalent amount of ... (c) p-fluorobenzonitrile,

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(d) p-methylbenzonitrile, (e) p-methoxybenzonitrile, (f) m-fluorobenzonitrile, (g) o-fluorobenzonitrile, or (h) o-methylbenzonitrile, Patent; Sandoz, Inc.; US4113727; (1978); (A1) English 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 The fluoroaromatic compounds resulting from carrying out the process of this invention using the illustrative chloroaromatic compounds (a) through (z) above are set forth below, followed by utilities for such resulting compounds: (a) 2-fluorobenzonitrile (b) 4-fluorobenzonitrile (c) 2-fluorobenzoyl chloride (d) 4-fluorobenzoyl chloride (e) 2-fluorobenzoyl fluoride (f) 4-fluorobenzoyl fluoride (g) 2-fluorobenzotrifluoride (h) 4-fluorobenzotrifluoride (i) tetrafluorobenzene ... Patent; MALLINCKRODT SPECIALTY CHEMICALS COMPANY; EP253838; (1991); (B1) English View in Reaxys Patent; MALLINCKRODT SPECIALTY CHEMICALS COMPANY; EP253837; (1991); (B1) English View in Reaxys Patent; MALLINCKRODT SPECIALTY CHEMICALS COMPANY; EP252964; (1991); (B1) English View in Reaxys ...presented by the following formula (4) which can respectively correspond to the formula (1) can be obtained. (D) Fluorine substituted aromatic compound represented by the formula (4) corresponding to the hydroxy compound wherein X1 is a substituent of the group (a) in the formula(1): ... 2,6-diphenylfluorobenzene, 4-phenoxyfluorobenzene,

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2-nitrofluorobenzene, 3-nitrofluorobenzene, 4-nitrofluorobenzene, 2,4-dinitrofluorobenzene, 2,5-dinitrofluorobenzene, 2,4,6-trinitrofluorobenzene, 2-cyanofluorobenzene, 3-cyanofluorobenzene, 4-cyanofluorobenzene, 2-chlorofluorobenzene, 3-chlorofluorobenzene, 4-chlorofluorobenzene, 2,4-dichlorofluorobenzene, 2,5-dichlorofluorobenzene, 2,6-dichlorofluorobenzene, 3,4-dichlorofluorobenzene, ... Patent; Mitsui Chemicals, Inc.; US6242654; (2001); (B1) English View in Reaxys 4.1.1.4.31 Patent; BOEHRINGER INGELHEIM INTERNATIONAL GMBH; HOFFMANN, Matthias; DAHMANN, Georg; FIEGEN, Dennis; HANDSCHUH, Sandra; KLICIC, Jasna; LINZ, Guenter; SCHAENZLE, Gerhard; SCHNAPP, Andreas; EAST, Stephen P.; MAZANETZ, Michael Philip; SCOTT, John; WALKER, Edward; WO2011/92128; (2011); (A1) English View in Reaxys 4

+ -4K

N (v6)

Fe N N

Rx-ID: 38673589 View in Reaxys 14/41 Yield

Conditions & References

92 %

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

42 %

13 : Example 13: Photocatalytic synthesis of compound 2-fluorobenzonitrile To a 25 mL screw test tube was added 0.25 mmol of 2-fluoroiodobenzene, 0.1 mmol of cyanide reagent 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 Solvent to the test tube, 500W visible light irradiation under the magnetic stirring reaction, control visible light intensity of 0.64W / cm2, the reaction Temperature of 55 ° C, 10 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 the liquid phase. The samples to be tested were compared with the 2-fluoroiodobenzene standard and the 2-fluorobenzonitrile standard. The conversion of the reaction substrate was 46.2percent, the selectivity of the target product was 100percent, and the liquid product yield was 46.2percent. 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-fluorobenzonitrile was obtained by column chromatography. The yield was 42percent With 3 Pd/CeO2, sodium acetate in N,N-dimethyl-formamide, isopropyl alcohol, Time= 10h, 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 O

F HO

F O

B HO

Rx-ID: 43101109 View in Reaxys 15/41 Yield 58 %

Conditions & References General procedure for the preparation of substituted benzonitriles (3a-3u)

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General procedure: To a 25 mL round flask was added the mixture of boronic acid (1) (0.3 mmol), ethyl2-cyano-3ethoxyacrylate (2a, 0.6 mmol), CuI (0.3 mmol), t-BuOOH (0.6 mmol) in DMF (2 mL)successively. The mixture was stirred at 130 °C for 24 h under air. After the reaction was completed, themixture was cooled to room temperature, diluted with water (15 mL) and then extracted withdichloromethane (5 mL × 3). The organic extract was washed with H2O (10 mL × 3) and dried overanhydrous Na2SO4. After removal of the CH2Cl2 in vacuum, the crude product thus obtained was purified bycolumn chromatography on silica gel using petroleum ether/ethyl acetate as eluent to give the desired product3 With tert.-butylhydroperoxide, copper(l) iodide in N,N-dimethyl-formamide, Time= 24h, T= 130 °C Qi, Chaorong; Hu, Xiaohan; He, Haitao; Synlett; vol. 27; nb. 13; (2016); p. 1979 - 1982; Art.No: ST-2016-W0122-L View in Reaxys O

F O

I N

Rx-ID: 43101141 View in Reaxys 16/41 Yield

Conditions & References

69 %

With tert.-butylhydroperoxide, copper(l) iodide in N,N-dimethyl-formamide, Time= 24h, T= 130 °C Qi, Chaorong; Hu, Xiaohan; He, Haitao; Synlett; vol. 27; nb. 13; (2016); p. 1979 - 1982; Art.No: ST-2016-W0122-L View in Reaxys N N

(v6)

Fe 4N

N3 H

H N

N N 4

K+

Rx-ID: 41405954 View in Reaxys 17/41 Yield

Conditions & References

86 %

Mono-Cyanation; General Procedure General procedure: To a vial (8 mL) were added Pd(OAc)2 (112 mg, 0.05 mmol), NHC 2(213 mg, 0.05 mmol), K4[Fe(CN)6]·3H2O (528 mg, 1.25 mmol), Na2CO3(530 mg, 5 mmol), and an aryl halide (5 mmol) under aerobic conditions.The mixture was stirred vigorously at 120 °C. Samples weretaken from the reaction mixture periodically, quenched with H2O, extractedwith EtOAc, and analyzed by GC–MS. After completion of thereaction, the mixture was allowed to cool to r.t., quenched with H2Oand extracted with EtOAc (3 × 15 mL). The combined extracts weredried (MgSO4) and the solvent was evaporated. The crude residue waspurified by column chromatography on silica gel (EtOAc–PE). With palladium diacetate, sodium carbonate, (1,3-bis(2,6-diisopropylphenyl)-4,5-dihydro-1Himidazol-2-ylidene)·HCl in DMAA, Time= 5h, T= 120 °C Xu, Zhicheng; Xiao, Yunqing; Ding, Hong; Cao, Changsheng; Li, Haitao; Pang, Guangsheng; Shi, Yanhui; Synthesis (Germany); vol. 47; nb. 11; (2015); p. 1560 - 1566; Art.No: SS-2014-F0771-OP View in Reaxys F

HO O

Rx-ID: 37873188 View in Reaxys 18/41 Yield 77 %

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

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Rx-ID: 35214710 View in Reaxys 19/41 Yield

Conditions & References

79 %, 6 %

Stage 1: With n-butyllithium in tetrahydrofuran, hexane, T= -28 °C , Flow reactor Stage 2: With N-fluoro-N-(phenylsulfonyl)benzene-sulfonamide in tetrahydrofuran, hexane, T= -28 °C , Flow reactor, Reagent/catalyst Nagaki, Aiichiro; Uesugi, Yuki; Kim, Heejin; Yoshida, Jun-Ichi; Chemistry - An Asian Journal; vol. 8; nb. 4; (2013); p. 705 - 708 View in Reaxys

F H 2N

N O

Rx-ID: 35229047 View in Reaxys 20/41 Yield

Conditions & References

82 %

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, Reagent/catalyst Garcia-Alvarez, Rocio; Diaz-Alvarez, Alba E.; Crochet, Pascale; Cadierno, Victorio; RSC Advances; vol. 3; nb. 17; (2013); p. 5889 - 5894 View in Reaxys F

F H 2N

N O

Rx-ID: 35307432 View in Reaxys 21/41 Yield

Conditions & References

82 %, 10 %Spectr.

With copper(II)-modified 4Å molecular sieve in acetonitrile, Time= 8h, T= 80 °C Kiss, Arpad; Hell, Zoltan; Synthetic Communications; vol. 43; nb. 13; (2013); p. 1778 - 1786 View in Reaxys 18F

I N

Rx-ID: 35885563 View in Reaxys 22/41 Yield

Conditions & References Reaction Steps: 2 1.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 0.25 h 1.2: 0.17 h 1.3: 14 h 2.1: 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane*(18)FK; potassium carbonate / N,N-dimethyl-formamide; water / 0.05 h / 150 °C With 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane*(18)FK, potassium carbonate, 3-chloro-benzenecarboperoxoic acid in dichloromethane, water, N,N-dimethyl-formamide Chun, Joong-Hyun; Telu, Sanjay; Lu, Shuiyu; Pike, Victor W.; Organic and Biomolecular Chemistry; vol. 11; nb. 31; (2013); p. 5094 - 5099 View in Reaxys

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O O

O–

I+ N

Rx-ID: 35885567 View in Reaxys 23/41 Yield

Conditions & References

96 %Chromat.

With 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane*(18)FK, potassium carbonate in water, N,N-dimethyl-formamide, Time= 0.0502778h, T= 150 °C , Temperature Chun, Joong-Hyun; Telu, Sanjay; Lu, Shuiyu; Pike, Victor W.; Organic and Biomolecular Chemistry; vol. 11; nb. 31; (2013); p. 5094 - 5099 View in Reaxys

F O

Rx-ID: 29286878 View in Reaxys 24/41 Yield

Conditions & References

74 %

With tetra-(n-butyl)ammonium iodide, triethylamine, bis(dibenzylideneacetone)-palladium(0), t-Bu-DPEphos in 1,4-dioxane, Time= 24h, T= 100 °C Murata, Miki; Sambommatsu, Tomoko; Oda, Takeshi; Watanabe, Shinji; Masuda, Yuzuru; Heterocycles; vol. 80; nb. 1; (2010); p. 213 - 218 View in Reaxys F

N F

Rx-ID: 9312405 View in Reaxys 25/41 Yield

Conditions & References

95.7 %

With 9,10-anthracenedione in N,N-dimethyl-formamide, Time= 8.25h, Electrochemical reaction Efremova; Podryvanova; Vasil'eva; Starichenko; Shteingarts; Russian Journal of Organic Chemistry; vol. 39; nb. 2; (2003); p. 212 - 218 View in Reaxys

(v2)

Rx-ID: 5321507 View in Reaxys 26/41 Yield

Conditions & References

85 %

With zinc, 1,1'-bis-(diphenylphosphino)ferrocene, tris(dibenzylideneacetone)dipalladium (0) in N,N-dimethyl acetamide, Time= 12h, T= 150 °C , Substitution Jin, Fuqiang; Confalone, Pat N.; Tetrahedron Letters; vol. 41; nb. 18; (2000); p. 3271 - 3273 View in Reaxys

Cl N

Br–

N P+

Rx-ID: 24427562 View in Reaxys 27/41

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Yield

Conditions & References

94%

3 : Preparation of 2-fluorobenzonitrile From 2-chlorobenzonitrile EXAMPLE 3 Preparation of 2-fluorobenzonitrile From 2-chlorobenzonitrile 137.5 g (1 mol) of 2-chlorobenzonitrile, 58 g (1 mol) of potassium fluoride, 5 g of nitrobenzene, 7.98 g of tetrakis(diethylamino)phosphonium bromide (phase transfer catalyst) and 30 ml of sulfolane are placed in a 500 ml four-neck flask fitted with thermometer, anchor stirrer and reflux condenser with bubble counter. The mixture is subsequently heated while stirring to 190° C. and allowed to react for 20 hours. After the reaction is complete, the reaction mixture is allowed to cool, dissolved in chlorobenzene, insoluble constituents are filtered off and the product (2-fluorobenzonitrile) is purified by fractional distillation under reduced pressure. Yield: 94percent Selectivity: 96percent Benzonitrile content: 0.1 percent With potassium fluoride in sulfolane, nitrobenzene, chlorobenzene Patent; Aventis Research and Technologies GmbH and Co KG; US6166242; (2000); (A1) English View in Reaxys

Br–

N N

N P+

Rx-ID: 24427563 View in Reaxys 28/41 Yield 90%

Conditions & References 11 : Preparation of 2-fluorobenzonitrile From 2-chlorobenzonitrile EXAMPLE 11 Preparation of 2-fluorobenzonitrile From 2-chlorobenzonitrile 137.5 g (1 mol) of 2-chlorobenzonitrile, 58 g (1 mol) of potassium fluoride, 5 g of phenyl methyl sulfoxide, 7.98 g of tetrakis(diethylamino)phosphonium bromide (phase transfer catalyst) and 30 ml of sulfolane are placed in a 500 ml four-neck flask fitted with thermometer, anchor stirrer and reflux condenser with bubble counter. The mixture is subsequently heated while stirring to 190° C. and allowed to react for 20 hours. After the reaction is complete, the reaction mixture is allowed to cool, dissolved in chlorobenzene, insoluble constituents are filtered off and the product (2-fluorobenzonitrile) is purified by fractional distillation under reduced pressure. Yield: 90percent Selectivity: 93percent Benzonitrile content: 0.08percent With potassium fluoride in sulfolane, chlorobenzene Patent; Aventis Research and Technologies GmbH and Co KG; US6166242; (2000); (A1) English View in Reaxys

O O

Rx-ID: 24970276 View in Reaxys 29/41 Yield

Conditions & References 3 : EXAMPLE 3 EXAMPLE 3 This Example is directed to the preparation of 2-fluorobenzonitrile in solvent by using the product of Example 2. 15 milliliters sulfolane, 3.2 grams(0.055 mole) spray-dried potassium fluoride, and 10.2 grams(0.055 mole) of the 2cyanobenzenesulfonyl fluoride prepared in Example 2 above were heated under nitrogen at 250° C. for one hour. The product was distilled directly from the resultant reaction mixture; the product weighed 5.6 grams and was identified by infrared spectroscopy as 2-fluorobenzonitrile. Based on 2-cyanobenzenesulfonyl fluoride, the per cent yield of 2-fluorobenzonitrile was 84. With potassium fluoride in sulfolane

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Patent; Allied-Signal Inc.; US5081275; (1992); (A1) English View in Reaxys 4 : EXAMPLE 4 EXAMPLE 4 This Example is directed to the preparation of 2-fluorobenzonitrile in the absence of solvent by using the product of Example 2. A mixture of 3.2 grams(0.055 mole) potassium fluoride, 10.2 grams(0.055 mole) of 2-cyanobenzenesulfonyl fluoride prepared in Example 2 above, and 0.1 gram dibenzo-18-crown-6 was stirred and heated under nitrogen at 225°-245° C. for two hours. The product was then vacuum distilled from the reaction mixture and weighed 2.9 grams. Based on 2-cyanobenzenesulfonyl fluoride, the per cent yield of 2-fluorobenzonitrile was 44. With potassium fluoride Patent; Allied-Signal Inc.; US5081275; (1992); (A1) English View in Reaxys F

–

N F

Rx-ID: 3124029 View in Reaxys 30/41 Yield

Conditions & References in N,N-dimethyl-formamide, kfr, Rate constant Efremova, N. V.; Starichenko, V. F.; Shteingarts, V. D.; Journal of Organic Chemistry USSR (English Translation); vol. 24; (1988); p. 47 - 56; Zhurnal Organicheskoi Khimii; vol. 24; nb. 1; (1988); p. 57 - 68 View in Reaxys

18F

N O

Rx-ID: 3569595 View in Reaxys 31/41 Yield 85 %

Conditions & References With Rb(18)F in dimethyl sulfoxide, Time= 0.333333h, T= 150 °C Attina, Marina; Cacace, Fulvio; Wolf, A. P.; Journal of the Chemical Society, Chemical Communications; nb. 3; (1983); p. 108 - 109 View in Reaxys F

Rx-ID: 1710038 View in Reaxys 32/41 Yield

Conditions & References gaseous plasma of glow discharge, Yield 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

Rx-ID: 1710040 View in Reaxys 33/41 Yield

Conditions & References gaseous plasma of glow discharge, Yield given. Yields of byproduct given

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So, Y. H.; Miller, Larry L.; Journal of the American Chemical Society; vol. 103; nb. 14; (1981); p. 4204 - 4209 View in Reaxys F N

Rx-ID: 2937805 View in Reaxys 34/41 Yield

Conditions & References With cobalt (III) fluoride in chloroform, Time= 18h, Heating, Product distribution Zweig, Arnold; Fischer, Robert G.; Lancaster, John E.; Journal of Organic Chemistry; vol. 45; nb. 18; (1980); p. 3597 - 3603 View in Reaxys

27 % Chromat., 62 % Chromat., 13 % Chromat.

With fluorine in trichlorofluoromethane, Time= 1h, T= -78 °C , competitive reaction with benzene, Rate constant, Product distribution Cacace, F.; Giacomello, P.; Wolf, A. P.; Journal of the American Chemical Society; vol. 102; nb. 10; (1980); p. 3511 - 3515 View in Reaxys

0.9 % Spectr., 0.7 % Spectr., 0.5 % Spectr.

With CsSO4F in acetonitrile, T= 25 °C , reagents ratio, presence of 1,3,5-trinitrobenzene, Product distribution, Rate constant Ip, Dominic P.; Arthur, Carol D.; Winans, Randall E.; Appelman, Evan H.; Journal of the American Chemical Society; vol. 103; nb. 8; (1981); p. 1964 - 1968 View in Reaxys

27 % Chromat., 13 % Chromat., 62 % Chromat.

With fluorine in trichlorofluoromethane, Time= 1h, T= -78 °C Cacace, F.; Giacomello, P.; Wolf, A. P.; Journal of the American Chemical Society; vol. 102; nb. 10; (1980); p. 3511 - 3515 View in Reaxys

F F

Rx-ID: 20511075 View in Reaxys 35/41 Yield

Conditions & References Reaction Steps: 2 1: gaseous plasma of glow discharge 2: gaseous plasma of glow discharge So, Y. H.; Miller, Larry L.; Journal of the American Chemical Society; vol. 103; nb. 14; (1981); p. 4204 - 4209 View in Reaxys Reaction Steps: 2 1: gaseous plasma of glow discharge 2: gaseous plasma of glow discharge So, Y. H.; Miller, Larry L.; Journal of the American Chemical Society; vol. 103; nb. 14; (1981); p. 4204 - 4209 View in Reaxys

F N

Rx-ID: 1710039 View in Reaxys 36/41

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Yield

Conditions & References

14 % Chromat., 17 % Chromat., 14 % Chromat., 4.0 % Chromat.

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

F F

F F F

Rx-ID: 2937808 View in Reaxys 37/41 Yield

Conditions & References

0.99 g, 0.28 g, 0.03 g, 0.22 g

0.03 g, 0.22 g, 0.28 g

With caesium tetrafluorocobaltate(III), Time= 1.5h, T= 300 °C , fluorination of benzonitriles over caesium tetrafluorocobaltate(III) at elevates temperatures, Product distribution Phull, Gurjeet S.; Plevey, Raymond G.; Rendell, Richard W.; Tatlow, John Colin; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1980); p. 1507 - 1511 View in Reaxys With caesium tetrafluorocobaltate(III), Time= 1.5h, T= 300 °C , Yields of byproduct given Phull, Gurjeet S.; Plevey, Raymond G.; Rendell, Richard W.; Tatlow, John Colin; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1980); p. 1507 - 1511 View in Reaxys With caesium tetrafluorocobaltate(III), Time= 1.5h, T= 300 °C , Yield given. Yields of byproduct given Phull, Gurjeet S.; Plevey, Raymond G.; Rendell, Richard W.; Tatlow, John Colin; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1980); p. 1507 - 1511 View in Reaxys F

monofluoroaromatics

Rx-ID: 6216107 View in Reaxys 38/41 Yield

Conditions & References With silver(II) fluoride in chloroform, Time= 18h, Heating, Product distribution Zweig, Arnold; Fischer, Robert G.; Lancaster, John E.; Journal of Organic Chemistry; vol. 45; nb. 18; (1980); p. 3597 - 3603 View in Reaxys Cl

2-chlorobenzonitrile (2ClBN)

Rx-ID: 25405227 View in Reaxys 39/41 Yield

Conditions & References 3 : EXAMPLE 3 EXAMPLE 3 A mixture of 2-chlorobenzonitrile, m.p. 93°, (200 g., 1.45 moles) and KF (99.9 g., 1.72 moles) in sulpholane (720 g., 5.85 moles) was kept at 240° for 20 hr. (slight reflux) in a 2 l. flanged flask fitted with a stainless steel stirrer, thermometer pocket and reflux condenser. The conversion of 2-chlorobenzonitrile (2ClBN) into 2-fluorobenzonitrile (2FBN) was 48percent after the first 9 hr. and 77percent after a total reaction time of 20 hr., according to g.l.c. analysis. With KF in tetramethylene sulfide

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Patent; I.S. C. Chemicals Limited; US4209457; (1980); (A1) English View in Reaxys

F N

Rx-ID: 25340351 View in Reaxys 40/41 Yield

Conditions & References 33 : EXAMPLE 33 EXAMPLE 33 The reaction described in Example 15 was carried out except that o-fluorotoluene was used in place of o-chlorotoluene. The contact time, the reaction temperature and the results were as follows. Contact time: 4.8 seconds Reaction temperature 440° C Conversion of o-fluoretoluene: 95.7percent Yield of o-fluorobenzonitrile: 84.7percent Patent; Nippon Kayaku Kabushiki Kaisha; US4124631; (1978); (A1) English View in Reaxys F

F H 2N

N O

Rx-ID: 348179 View in Reaxys 41/41 Yield

Conditions & References With thionyl chloride Borsche; Wagner-Roemmich; Justus Liebigs Annalen der Chemie; vol. 546; (1941); p. 273,275 View in Reaxys

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