1.2 CYC-CH=C[(CH3)x(1–3)]-NO2 to CYC-CH2-C(=O)[(CH3)x(1–3)] by Asch

Reactions (210)

Yield

Substances (373)

Conditions

Citations (138)

References

100

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T=100°C; 2 h;

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Rx-ID: 33838038

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Bruce, Ian; Akhlaq, Mohammed; Bloomfield, Graham C.; Budd, Emma; Cox, Brian; Cuenoud, Bernard; Finan, Peter; Gedeck, Peter; Hatto, Julia; Hayler, Judy F.; Head, Denise; Keller, Thomas; Kirman, Louise; Leblanc, Catherine; Grand, Darren Le; McCarthy, Clive; O'Connor, Desmond; Owen, Charles; Oza, Mrinalini S.; Pilgrim, Gaynor; Press, Nicola E.; Sviridenko, Lilya; Whitehead, Lewis

Bioorganic and Medicinal Chemistry Letters, 2012 , vol. 22, # 17 p. 5445 - 5450 Title/Abstract Full Text View citing articles Show Details

101

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Rx-ID: 3258543

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72%

With hydrogenchloride; iron(III) chloride; iron in methanol; water

4 h; Heating;

Sircar; Duell; Bristol; Weishaar; Evans

Journal of Medicinal Chemistry, 1987 , vol. 30, # 6 p. 1023 - 1029 Title/Abstract Full Text View citing articles Show Details

102

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With hydrogenchloride; iron(III) chloride; iron

1 h; Heating;

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Rx-ID: 1065791

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Binovic,K.; Vrancea,S.

Chimica Therapeutica, 1968 , vol. 3, p. 313 - 320 Full Text View citing articles Show Details

103

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With hydrogenchloride; iron(III) chloride; iron

1 h; Heating;

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Rx-ID: 1065795

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Binovic,K.; Vrancea,S.

Chimica Therapeutica, 1968 , vol. 3, p. 313 - 320 Full Text View citing articles Show Details

104

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92%

With hydrogenchloride; iron in methanol; water

0.5 h; Heating;

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Rx-ID: 9827263

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Pradhan, Prasun K.; Dey, Sumit; Jaisankar, Parasuraman; Giri, Venkatachalam S.

Synthetic Communications, 2005 , vol. 35, # 7 p. 913 - 922 Title/Abstract Full Text View citing articles Show Details

105

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Rx-ID: 25033467

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With hydrogenchloride in methanol; water

Hide Experimental Procedure

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A. Nattermann and Cie GmbH

Patent: US4699914 A1, 1987 ; Title/Abstract Full Text Show Details

4.b:1-[4-(1-imidazolyl)-2-thienyl]-2-propanone

(b) 1-[4-(1-imidazolyl)-2-thienyl]-2-propanone A mixture of 34 g (1-[2-(2-nitro-1-propenyl)-4-thienyl]-imidazole, 65 g iron powder, 0.9 ferrichloride hexahydrate, 51 ml methanol and 100 ml water are heated to reflux temperature while stirring. At this temperature, 65 ml concentrated hydrochloric acid are added dropwise within 1 hour. Subsequently, stirring is continued for 11/2 hours under reflux. After cooling, the mixture is stirred into 4 times the amount of methanol. Then, it is filtrated. The filtrate is evaporated to about 1/5 of its volume and filled up with water to 500 ml. The precipitated brown deposit is sucked off, then the filtrate is extracted several times with dichloromethane. The united dichloromethane phases are dried and evaporated. The residual crude product is used in the following reaction steps without further purification. Yield: 10g of brown oil.

106

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With hydrogenchloride; iron(III) chloride; iron

107

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Patent: US2771469 , 1953 ; Full Text Show Details

Rx-ID: 418770

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With hydrogenchloride; iron(III) chloride; iron

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Rx-ID: 1043509

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Schultz,E.M. et al.

Journal of Medicinal Chemistry, 1967 , vol. 10, p. 717 - 724 Full Text View citing articles Show Details

108

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Rx-ID: 25259227

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With iron(III) chloride; iron; acetic acid in hydrogenchloride; water; acetone

Clin Midy

Patent: US3953442 A1, 1976 ;

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Title/Abstract Full Text Show Details

1.c:c.

c. 5-chloro-3-(2-oxopropyl)indole A mixture of 104g of 5-chloro-3-(2-nitropropen-1-yl)indole, 115g of powdered iron and 6g of ferric chloride dissolved in 1250 ml of acetone is brought to reflux. Heating ceases as soon as reflux commences and a solution of 265 ml of acetic acid in 800 ml of water is added over 30 minutes. The reaction mixture is again brought to reflux and maintained thereat for 4 hours; 25.6g of sodium bisulphite are then added, the mixture cooled to 20°C and filtered. The residue is washed with acetone. The combined filtrate and washings are concentrated after filtering and redissolved in 105 ml of hydrochloric acid and 520 ml of water, extracted with ethyl acetate, washed and dried. 87.5 g of oil are obtained by concentration B.pt: 183°-198°C/0.3 m.m. Weight of product 63.4 g.

109

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80%

With hydrogenchloride; iron(III) chloride; iron in ethanol; water

3 h; Heating;

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Rx-ID: 3139635

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Takeya; Okubo; Nishida; Tobinaga

Chemical and Pharmaceutical Bulletin, 1985 , vol. 33, # 9 p. 3599 - 3607 Title/Abstract Full Text View citing articles Show Details

110

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With perchloric acid; iron

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Rx-ID: 1084426

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Aldous,F.A.B. et al.

Journal of Medicinal Chemistry, 1974 , vol. 17, p. 1100 - 1111 Full Text View citing articles Show Details

(i) H2, Pd-C, EtOH, (ii) HCl, Et2O; Multistep reaction;

Coutts; Malicky

Canadian Journal of Chemistry, 1974 , vol. 52, # 3 p. 395 - 399 Title/Abstract Full Text View citing articles Show Details

With iron; acetic acid

Matin,S.B. et al.

Journal of Medicinal Chemistry, 1974 , vol. 17, p. 877 - 882 Full Text View citing articles Show Details

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111

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Rx-ID: 8610215

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B: 78%

With indium; chloro-trimethyl-silane

T=25°C; Reduction; Addition; 5.5 h;

Yadav; Subba Reddy; Srinivas; Ramalingam

Synlett, 2000 , # 10 p. 1447 - 1449 Title/Abstract Full Text View citing articles Show Details

112

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Rx-ID: 22727904

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Multi-step reaction with 3 steps 1: H2 / Pd-C / ethanol 2: aq. HNO3, NaNO2 / acetic acid 3: H2, aq. HCl / Pd-C / ethanol View Scheme

Coutts; Malicky

Canadian Journal of Chemistry, 1973 , vol. 51, # 9 p. 1402 - 1409 Title/Abstract Full Text View citing articles Show Details

113

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50%

With sodium tetrahydroborate; dihydrogen peroxide; potassium carbonate in methanol

20 h; Ambient temperature;

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Rx-ID: 3707490

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Ballini; Bosica

Synthesis, 1994 , # 7 p. 723 - 726 Title/Abstract Full Text View citing articles Show Details

114

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With hydrogenchloride; water; anhydrous iron chloride; iron

8 h; Heating / reflux; Hide Experimental Procedure

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Rx-ID: 27757429

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NOVARTIS AG

Patent: WO2008/52733 A1, 2008 ; Location in patent: Page/Page column 62 ; Title/Abstract Full Text Show Details

8.2:

Staqe 8.2: 1 -(4-Methanesulfonyl-phenyl)-propan-2-one4-Methanesulfonyl-benzaldehyde (1.75 g; 9.02 mmol), nitroethan (5.24 ml; 72.2 mmol) and ammonium acetate (211 mg; 2.71 mmol) are heated for 5 h at 125°C. The excess reagent is removed by evaporation on a rotavap, then CH2CI2 is added, and the mixture is washed with water and brine. After drying over Na2SO4, the solvent is removed and thereafter the 1- methanesulfonyl-2-nitro-propenyl)-benzene intermediate is suspended in 11 ml of water. Iron powder (1.98 g; 35.2 mmol) and FeCI3 '6H2O (48.8 mg; 0.18 mmol) are added, and the mixture is heated to reflux. At that temperature, 5 ml

of 2M HCI is added slowly during 1 h and the reaction is run for additional 7 h at reflux. To the cold reaction mixture, CH2CI2 is added and filtered over hyflo. The organic phase is separated, washed with water and brine and dried over Na2SO4. After evaporation of the solvent, the title compound is obtained. HPLC: tR = 3.21 min.; ES-MS: 211 (M-1).

With iron; acetic acid

T=100°C;

Bioorganic and Medicinal Chemistry Letters, 2012 , vol. 22, # 17 p. 5445 - 5450 Title/Abstract Full Text View citing articles Show Details

115

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Rx-ID: 27757433

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Stage #1: With acetic acid; iron

T=60 - 105°C; Stage #2: With water

NOVARTIS AG

Patent: WO2008/52733 A1, 2008 ; Location in patent: Page/Page column 72; 73 ;

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Title/Abstract Full Text Show Details

30.5:

Stage 30.5: 1 -(2-Chloro-4-methoxy-5-methyl-phenyl)-propan-2-one The title compound is prepared in a slightly different way as the compound prepared in Stage 8.2: 5 g (13.5 mmol) of 2-chloro-4-methoxy-5-methyl-benzaldehyde (see Stage 30.4.) and 316 mg (4.06 mmol) of NH4OAc in 7.86 ml of nitroethane are heated overnight at 125°C EPO <DP n="74"/>The reaction mixture is concentrated under reduced pressure. The residue is dissolved in CH2CI2 and extracted with H2O. The aqueous phase is washed with CH2CI2. The combined organic phases are washed with brine, dried, and evaporated to dryness. A 5-necked flask is charged with 3.04 g (54.2 mmol) of iron powder and 8.5 ml of HOAc. The flask is fitted with a condenser and the mixture is stirred at 600C to form a grey slurry. To the slurry a suspension of the above intermediate in glacial HOAc is added slowy, and then stirred overnight at 1050C. The reaction is allowed to cool down and is poured onto H2O. The

suspension is filtered over hyflo. The layers are separated and the organic phase washed with 1 N HCI, sat. NaHCO3, water, and brine. The solvent is evaporated, and the residue purified by flash chromatography (solvent system: hexane-EtOAc 100:0 to 50:50). The product is isolated as an oil. MS.: 213 (M+1).- HPLC: tR = 6.29 min.

116

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With hydrogenchloride; iron(III) chloride; iron

1 h; Heating;

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Rx-ID: 1062903

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Binovic,K.; Vrancea,S.

Chimica Therapeutica, 1968 , vol. 3, p. 313 - 320 Full Text View citing articles Show Details

117

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With hydrogenchloride; iron(III) chloride; iron

1 h; Heating;

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Rx-ID: 1063060

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Binovic,K.; Vrancea,S.

Chimica Therapeutica, 1968 , vol. 3, p. 313 - 320 Full Text View citing articles Show Details

118

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Rx-ID: 1074695

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82%

With L-Selectridereg; in tetrahydrofuran

0.5 h;

Mourad, M. Soubei; Varma, Rajender S.; Kabalka, George W.

Synthesis, 1985 , # 6/7 p. 654 - 656 Title/Abstract Full Text Show Details

With hydrogenchloride; iron(II) chloride in ethanol

Ferreira,A.B.B.; Salisbury,K.

Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1978 , p. 995 - 1001 Full Text View citing articles Show Details

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With hydrogenchloride; iron(III) chloride; iron

1 h; Heating;

Binovic,K.; Vrancea,S.

Chimica Therapeutica, 1968 , vol. 3, p. 313 - 320 Full Text View citing articles Show Details

Hide Details

With hydrogenchloride; iron

Nelson,K.L. et al.

Journal of the American Chemical Society, 1964 , vol. 86, p. 684 - 687 Full Text View citing articles Show Details

77 % Chromat.

With sodium hypophosphite; nickel in ethanol; water

T=40 - 60°C; 2 h;

Monti, Diego; Gramatica, Paola; Speranza, Giovanna; Manitto, Paolo

Tetrahedron Letters, 1983 , vol. 24, # 4 p. 417 - 418 Title/Abstract Full Text View citing articles Show Details

With iron; acetic acid

T=100°C; 2 h;

Cloonan, Suzanne M.; Keating, John J.; Butler, Stephen G.; Knox, Andrew J.S.; Jorgensen, Anne M.; Peters, Guenther H.; Rai, Dilip; Corrigan, Desmond; Lloyd, David G.; Williams, D. Clive; Meegan, Mary J.

European Journal of Medicinal Chemistry, 2009 , vol. 44, # 12 p. 4862 - 4888 Title/Abstract Full Text View citing articles Show Details

119

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79%

With chromium dichloride in tetrahydrofuran; hydrogenchloride

4 h; Heating;

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Rx-ID: 2153008

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Varma, Rajender S.; Varma, Manju; Kabalka, George W.

Tetrahedron Letters, 1985 , vol. 26, # 32 p. 3777 - 3778 Title/Abstract Full Text View citing articles Show Details

120

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Stage #1: With sodium tetrahydroborate in methanol

T=20°C; Nef Reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol

T=20°C; 18 h; Hide Experimental Procedure

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Rx-ID: 35934210

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Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron, 2013 , vol. 69, # 30 p. 6129 - 6143 Title/Abstract Full Text View citing articles Show Details

4.3.18 Ethyl (2S)-2-(2-oxopropyl)piperidine-1-carboxylate (18c).

General procedure: Following the general procedure II, compound 21c (0.24 g, 1.0 mmol) on Nef reaction gave 18c (0.13 g, 60percent) as a pale yellow viscous liquid.

121

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T=120°C; 2 h; Hide Experimental Procedure

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Rx-ID: 24733628

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GLAXO GROUP LIMITED

Patent: WO2006/94799 A2, 2006 ; Location in patent: Page/Page column 59-60 ; Title/Abstract Full Text Show Details

71-73: To a suspension of iron powder (5.2g) in AcOH (28 mL) was added dropwise a solution of Intermediate 70 (2.2 g) in AcOH (18mL). The mixture was heated at 12O0C for 2h, diluted with water and extracted with CH2CI2. The organic layer was dried over Na2SO4 and concentrate to dryness to afford 1.6g of Intermediate 71 , as a

dark solid which was not further purified. Intermediate 71 was dissolved in Ac2O (4mL) and dropped onto a solution of Eaton's reagent (7mL) and Ac2O (3.6mL). The mixture was heated at 500C for 1h. EPO <DP n="61"/>Water and diethylether (Et2O) were added, the organic layer was dried over Na2SO4 and evaporated under reduced pressure to afford Intermediate 72, which not further purified. Crude Intermediate 72 was dissolved ethanol (25 ml) and commercial 30percent aqueous ammonia (75ml) was added. The mixture was heated at 14O0C in a steel reactor for 8h, then allowed to cool to room temperature overnight. The solvent was evaporated under reduced pressure and the crude product was purified by column chromatography on silica gel (eluent: CH2CI2/CH3OH, 10:1) to give 0.3 g of the title compound. 1H NMR (δ, ppm, DMSO-d6): 11.22 (s, 1H), 8.67 (d, 1H), 7.98 (dd, 1H), 7.39 (d, 1 H), 5.97 (s, 1H), 2.19 (S, 3H)1 2.12 (s, 3H)

122

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Rx-ID: 23236743

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With hydrogenchloride; 4ClO4(1-)*Fe(3+) in water

8.5 h; Heating / reflux; Hide Experimental Procedure

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Leonardi, Amedeo; Motta, Gianni; Riva, Carlo; Poggesi, Elena

Patent: US2004/72839 A1, 2004 ; Location in patent: Page/Page column 20 ; Title/Abstract Full Text Show Details

1-(2-Trifluoromethoxyphenyl)propan-2-one (Compound 2a) A solution of 1.9 g of 1-(2-trifluoromethoxy)benzaldehyde, 4 ml of EtOH, 1.3 ml of 96percent 2-nitroethane and 0.10 ml of n-butylamine was stirred at reflux for 18 h. Afterwards, it was diluted with H2O, extracted with EtOAc (2?30 ml), washed with H2O (2?30 ml), brine, dried (Na2SO4) ed evaporated in vacuo to afford 2.47 g of an orange oil, which was purified by flash chromatography (PE-EtOAc 100:5). Evaporation of the collected fractions yielded 1.60 g of 2-nitro-3-(2-trifluoromethoxyphenyl)prop-2-ene as a pale yellow oil. 1H-NMR (CDCl3, ?): 2.35 (s, 3H), 7.30-7.55 (m, 4H), 8.10 (s,1H) A mixture of 1.6 g of the above compound, 0.024 g of Fe(ClO4)3, 3.0 g of Fe, 6 ml of H2O was heated at reflux and stirred for 7.5 h. After overnight resting at r.t., was added 2.80 ml of 37percent HCl, heating for 1 h. After cooling, the mixture was extracted with EtOAc (3?40 ml), which was dried (Na2SO4) ed evaporated in vacuo to give the title compound (g 1.28) as an orange oil. 1H-NMR (CDCl3, ?): 2.22 (s, 3H), 3.77 (s, 2H), 7.15-7.40 (m, 4H) 4-Oxo-3-(2-trifluoromethoxyphenyl)pentanal diethyl acetal (Compound 2b) To a suspension of 1.87 g of 60percent NaH oil dispersion in 10 ml of anhydrous DMF was added dropwise during 6 min under a nitrogen stream, a solution of compound 2a in 15 ml of DMF and the reaction mixture was stirred at r.t. for 3 h. After overnight resting, was added 0.447 g of 2-bromoacetaldehyde diethyl acetal (97percent) in 5 ml of DMF; the mixture was stirred at r.t. for 30?, then at 80 C. for 3 h. Afterwards, the mixture was diluted with H2O (250 ml), acidified with HCl 2N, extracted with Et2O (3?50 ml), washed with H2O (40 ml), dried (Na2SO4) and evaporated in vacuo, affording a crude (brownish oil), which was purified by flash chromatography (PE-EtOAc 100:2) to yield 1.44 g of compound 2b as a yellowish oil. 1H-NMR (CDCl3, ?): 1.08-1.32 (m, 6H), 1.75-1.95 (m, 1H), 2.08 (s, 3H), 2.35-2.60 (m, 1H), 3.20-3.80 (m, 4H), 4.20-4.40 (2H), 7.15-7.35 (4H) 4-Oxo-3-(2-trifluoromethoxyhenyl)pentanal (Compound 2c) The title compound was obtained following the procedure described for Compound 1e but using as a starting material Compound 2b instead of Compound 1d. After the usual work-up procedure, the title compound was obtained (99percent) and used without further purification in the next step. 1H-NMR (CDCl3, ?): 2.12 (s, 3H), 2.58 (dd, 1H), 3.40 (dd, 1H), 4.61 (dd, 1H), 7.11-7.40 (m, 4H), 9.75 (s, 1H) 1-(4-Fluoro-2-methoxyphenyl)-4-[4-Oxo-3-(2-trifluoromethoxyphenyl)pentyl]piperazine The title compound was obtained following the procedure described for the Compound of Example 1, but using as a starting material Compound 2c instead of compound 1e and 1-(4-fluoro-2-methoxyphenyl)piperazine instead of 1-(2,2,2-trifluoroethoxyphenyl)piperazine. Purification by flash chromatography (PE-EtOAc 7:3) yielded the title compound (60percent). Oil. 1H-NMR (CDCl3, ?): 1.65-1.85 (m, 1H), 2.10 (s, 3H), 2.25-2.45 (m, 3H), 2.50-2.70 (m, 4H), 2.85-3.10 (m, 4H), 3.82 (s, 3H), 4.15-4.31 (m, 1H), 6.50-6.68 (m, 2H), 6.78-6.90 (m, 1H), 7.20-7.35 (m, 4H)

123

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Rx-ID: 25272661

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55%

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With hydrogenchloride; iron(III) chloride in diethyl ether; water

Synthelabo

Patent: US3965190 A1, 1976 ;

Hide Experimental Procedure

Title/Abstract Full Text Show Details

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6:1-(3'-Trifluoromethoxy-phenyl)-2-propanone.

EXAMPLE 6 1-(3'-Trifluoromethoxy-phenyl)-2-propanone. 29g (117 mmols) of 1-(3'-trifluoromethoxy-phenyl)-2-nitro-propene, 46g (0.82g atom) of iron powder, 0.6g. of ferric chloride and 120 ml of water are introduced into a 500 ml. threenecked flask equipped with a mechanical stirrer, a condenser and a dropping funnel, and this mixture is heated at 80°C. 29 ml. of concentrated hydrochloric acid are added dropwise, via the dropping funnel, with stirring, over the course of 5 hours, while the temperature is kept at 80°C. The reaction mixture is allowed to cool overnight. The ketone is then steam distilled. The distillate is extracted twice in succession with 100 ml. of diethyl ether each time. The two ether extracts are combined, dried over sodium sulphate and filtered. The solvent is evaporated from the filtrate in vacuo on a water bath, and the residue is rectified. 14,15g (55 percent yield) of 1-(3'-trifluoromethoxy-phenyl)-2-propanone are thus obtained as a liquid, b.p. 112°-118°C./18mm.Hg., nD21 °5 = 1.448

55%

With hydrogenchloride; iron(III) chloride in diethyl ether; water

Synthelabo

Patent: US4129598 A1, 1978 ;

Hide Experimental Procedure

Title/Abstract Full Text Show Details

2.c:(c)

(c) 1-(3'-Trifluoromethoxy-phenyl)-2-propanone. 29 g (117 mmols) of 1-(3'-trifluoromethoxyphenyl)-2-nitro-propene, 46g (0.82 g atom) of iron powder, 0.6 g of ferric chloride and 120 ml of water are introduced into a 500 ml three-necked flask equipped with a mechanical stirrer, a condenser and a dropping funnel, and this mixture is heated at 80° C. 29 ml of concentrated hydrochloric acid are added dropwise, via the dropping funnel, with stirring, over the course of 5 hours, while the temperature is kept at 80° C. The reaction mixture is allowed to cool overnight. The ketone is then steam distilled. The distillate is extracted twice in succession with 100 ml of diethyl ether each time. The two ether extracts are combined, dried over sodium sulphate and filtered. The solvent is evaporated from the filtrate in vacuo on a water bath, and the residue is rectified. 14, 15 g (55 percent yield) of 1-(3'-trifluoromethoxy-phenyl)-2-propanone are thus obtained as a liquid, b.p. 112° -118° C/18 mm.Hg, nD21°5 = 1.448.

124

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Rx-ID: 28113970

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Stage #1: 2-nitro-3-(2-trifluoromethoxyphenyl)-prop-2ene With iron; iron (III) perchlorate in water

7.5 h; Heating / reflux; Stage #2: hydrogenchloride in water

1 h; Heating / reflux; Hide Experimental Procedure

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RECORDATI S.A.; RECORDATI INDUSTRIA CHIMICA E FARMACEUTICA SpA

Patent: WO2003/106443 A1, 2003 ; Location in patent: Page 36 ; Title/Abstract Full Text Show Details

A mixture of 1.6 g of the above compound, 0.024 g of Fe [(C104)] 3,3. 0 g of Fe, 6 ml of H20 was heated at reflux and stirred for 7.5 h. After overnight resting at r. [T.,] was added 2.80 ml of 37percent HCl, heating for 1 h. After cooling, the mixture was extracted with EtOAc [(3X40] [ML),] which was dried [(Na2S04)] ed evaporated in vacuo to give the title compound (g 1.28) as an orange oil. 'H-NMR (CDCl3, δ) : 2.22 (s, 3H), 3.77 (s, 2H), 7.15-7. 40 (m, 4H)

125

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With hydrogenchloride; water; iron in methanol

T=65°C; Hide Experimental Procedure

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Rx-ID: 23066649

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Takeda Chemical Industries, Ltd.

Patent: EP1447402 A1, 2004 ; Location in patent: Page 67, 68 ; Title/Abstract Full Text Show Details

73:

Reference Example 73 methyl 4-(2-oxopentyl)benzoate To a solution (82 ml) of methyl 4-[(1Z)-2-nitropenta-1-enyl]benzoate (5.50 g, 22.0 mmol) obtained in Reference Example 72 and iron powder (7.40 g, 132 mmol) in methanol was added dropwise conc. hydrochloric acid (37.0 ml) at 65°C, and the mixture was stirred at 65°C for 4 hrs.. The solvent was evaporated under reduced pressure.. water was added to the residue, and the mixture was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate.. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (eluding solvent; hexane:ethyl acetate = 4: 1) to give the title compound (2.53 g) as a pale-yellow liquid.1H-NMR (CDCl3) δ: 0.88 (3H, t, J=7.3Hz), 1.59 (2H, m), 2.44 (2H, t, J=7.3Hz), 3.74 (2H, s), 3.91 (3H, s), 7.27 (2H, m), 7.99 (2H, dt, J=8.5, 1.9Hz).

126

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Hide Experimental Procedure

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Rx-ID: 25054547

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Beecham Group P.L.C.

Patent: US4622342 A1, 1986 ; Title/Abstract Full Text Show Details

1-(4-n Pentyloxyphenyl)propan-2-one

1-(4-n Pentyloxyphenyl)propan-2-one The title compound, bp 140°-150°/1.5 mm, was prepared from 1-(4-n pentyloxyphenyl)-2-nitroprop-1-ene, by an analogous procedure to that described in Description 5. 1 Hnmr τ(CDCl ): 8.05-9.3 (9H, complex), 7.9 (3H, s), 6.4 (2H, s), 6.1 (2H, t), 2.7-3.3 (4H, dd). 3

127

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78%

With chromium dichloride in tetrahydrofuran; hydrogenchloride

4 h; Heating;

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Rx-ID: 2200380

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Varma, Rajender S.; Varma, Manju; Kabalka, George W.

Tetrahedron Letters, 1985 , vol. 26, # 32 p. 3777 - 3778 Title/Abstract Full Text View citing articles Show Details

128

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With hydrogenchloride; iron

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Rx-ID: 4304588

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Nichols; Barfknecht; Rusterholz; Benington; Morin

Journal of medicinal chemistry, 1973 , vol. 16, # 5 p. 480 - 483 Title/Abstract Full Text View citing articles Show Details

129

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(i) Fe, FeCl3, H2O, (ii) aq. HCl; Multistep reaction;

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Rx-ID: 4306526

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Standridge; Howell; Gylys; et al.

Journal of Medicinal Chemistry, 1976 , vol. 19, # 12 p. 1400 - 1404 Title/Abstract Full Text View citing articles Show Details

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130

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Rx-ID: 8610386

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B: 84%

With indium; chloro-trimethyl-silane

T=25°C; Reduction; Addition; 4 h;

Yadav; Subba Reddy; Srinivas; Ramalingam

Synlett, 2000 , # 10 p. 1447 - 1449 Title/Abstract Full Text View citing articles Show Details

131

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With hydrogenchloride; iron in methanol

Hide Experimental Procedure

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Rx-ID: 24891093

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Bayer Aktiengesellschaft

Patent: US5028617 A1, 1991 ; Title/Abstract Full Text Show Details

[2-(2-Ethoxyethoxy)-5-pyridyl]acetone

[2-(2-Ethoxyethoxy)-5-pyridyl]acetone 6.5 ml of concentrated hydrochloric acid are added dropwise to a boiling suspension of 800 mg (3.2 mmol) of 1-[2-(2-ethoxyethoxy)-5-pyridyl]-2-nitro-1-propene and 710 mg of iron filings in 10 ml of methanol. After 30 minutes the mixture is filtered and diluted with water.

It is washed with ether, adjusted to pH 7 and extracted with ether. The organic phase is washed with 1percent strength aqueous sodium hydroxide solution and then with water, dried over sodium sulphate and evaporated. 420 mg (60percent of theory) of a pale yellow oil are obtained. 1 H NMR (CDCl , δ [ppm]): 1.2 (t, 3H); 2.2 (s, 3H); 3.55 (q, 2H); 3.7 (s, 2H); 3.8 (m, 2H); 4.5 (m, 2H); 6.8 (d, 1H); 7.4 (dd, 1H); 8.0 (d, 1H). 3

132

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With hydrogenchloride; iron(III) chloride; iron in water

4 h; Heating; Yield given;

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Rx-ID: 3138200

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Werbel; Cook; Elslager; Hung; Johnson; Kesten; McNamara; Ortwine; Worth

Journal of Medicinal Chemistry, 1986 , vol. 29, # 6 p. 924 - 939 Title/Abstract Full Text View citing articles Show Details

133

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With hydrogen; acetic acid; nickel

T=25°C; 15 h;

Rosowsky, Andre; Mota, Clara E.; Wright, Joel E.; Freisheim, James H.; Heusner, James J.; et al.

Journal of Medicinal Chemistry, 1993 , vol. 36, # 21 p. 3103 - 3112 Title/Abstract Full Text View citing articles Show Details

With hydrogenchloride; iron(III) chloride; iron

Biel et al.

Journal of the American Chemical Society, 1959 , vol. 81, p. 2805,2810, 2813 Full Text View citing articles Show Details

134

Rx-ID: 363750

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65%

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With hydrogenchloride; iron(III) chloride; iron in toluene

Heating;

Frost,D.A.; Morrison,G.A.

Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1973 , p. 2388 - 2396 Full Text View citing articles Show Details

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Rx-ID: 2049848

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80.5%

With hydrogenchloride; anhydrous iron chloride; water; iron in toluene

6 h; Reflux;

Neudoerffer, Anne; Mueller, Melanie; Martinez, Claire-Marie; Mechan, Annis; McCann, Una; Ricaurte, George A.; Largeron, Martine

Chemical Research in Toxicology, 2011 , vol. 24, # 6 p. 968 - 978 Title/Abstract Full Text View citing articles Show Details

75%

With iron in acetic acid

3 h; Heating;

Musson; Karashima; Rubiero; Melmon; Cheng; Castagnoli Jr.

Journal of Medicinal Chemistry, 1980 , vol. 23, # 12 p. 1318 - 1323 Title/Abstract Full Text View citing articles Show Details

135

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Rx-ID: 2158821

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80%

With hydrogenchloride; iron(III) chloride; iron in ethanol; water

3 h; Heating;

Takeya; Okubo; Nishida; Tobinaga

Chemical and Pharmaceutical Bulletin, 1985 , vol. 33, # 9 p. 3599 - 3607 Title/Abstract Full Text View citing articles Show Details

80%

With hydrogenchloride; iron in methanol; water

0.5 h; Heating;

Pradhan, Prasun K.; Dey, Sumit; Jaisankar, Parasuraman; Giri, Venkatachalam S.

Synthetic Communications, 2005 , vol. 35, # 7 p. 913 - 922 Title/Abstract Full Text View citing articles Show Details

57%

With hydrogenchloride; iron(III) chloride; iron in ethanol; water

3 h; Heating;

Carroll, Anthony R.; Krauss, Adrian S.; Taylor, Walter C.

Australian Journal of Chemistry, 1993 , vol. 46, # 3 p. 277 - 292 Title/Abstract Full Text Show Details

136

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With hydrogenchloride; iron(III) chloride; iron

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Rx-ID: 4220134

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Seidl,G. et al.

Justus Liebigs Annalen der Chemie, 1964 , vol. 677, p. 34 - 46 Full Text View citing articles Show Details

137

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94%

With iron in acetic acid

T=20°C; 0.5 h;

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Rx-ID: 42194378

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Sathish, Manda; Chetna, Jadala; Hari Krishna, Namballa; Shankaraiah, Nagula; Alarifi, Abdullah; Kamal, Ahmed

Journal of Organic Chemistry, 2016 , vol. 81, # 5 p. 2159 - 2165 Title/Abstract Full Text View citing articles Show Details

138

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88%

With iron; acetic acid

Heating;

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Rx-ID: 3478663

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Jacob III; Shulgin

Journal of Medicinal Chemistry, 1983 , vol. 26, # 5 p. 746 - 752 Title/Abstract Full Text View citing articles Show Details

139

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2.53 g

With water; hydrogen; acetic acid in methanol

T=50°C; Hide Experimental Procedure

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Rx-ID: 36292759

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NOVARTIS AG; CROWE, Michael; FOULKES, Michael; FRANCESE, Giancarlo; GRIMLER, Dominique; KUESTERS, Ernst; LAUMEN, Kurt; LI, Yunzhong; LIN, Changxue; NAZOR, Jovana; RUCH, Thomas; SMITH, Derek; SONG, Shiwei; TENG, Shangjun

Patent: WO2013/139987 A1, 2013 ; Location in patent: Page/Page column 93 ; Title/Abstract Full Text Show Details

3:1 -(6-ChIoro-5-f Iuoro-1 H-indol-3-yl)-propan-2-one

Raney/Ni (0.75g) and acetic acid (1.1 mL, 19.6 mmol) were charged to the suspension of 6-Chloro-5-fluoro-3-((Z)-2-nitro-propenyl)-1 H-indole (5g, 19.6 mmol) in the mixture of MeOH and H20 (2:1 , 50 mL) at r.t. The reaction mixture vacuumed and purged with H2 three times and heated at 50 °C for overnight. MeOH (50 mL) was added to the reaction mixture and the catalyst was filtered off over celite. The solvent was concentrated to 50 mL and H20 (300 ml) was added. With the addition of H20, off-white solid was produced. The solid was filtered and washed by water. After dried in the oven, 2.53 g off-white solid was isolated.

Multi-step reaction with 2 steps 1: platinum on carbon; hydrogen / ethyl acetate / 20 °C / |Inert atmosphere 2: water; sodium hydrogensulfite / ethanol / 80 °C View Scheme

Patent: WO2013/139987 A1, 2013 ;

With sodium hydrogensulfite in ethanol; water; ethyl acetate

Novartis AG; Crowe, Michael; Foulkes, Michael; Francese, Giancarlo; Grimler, Dominique; Kuesters, Ernst; Laumen, Kurt; Li, Yunzhong; Lin, Changxue; Nazor, Jovana; Ruch, Thomas; Smith, Derek; Song, Shiwei; Teng, Shangjun

Patent: US2015/45562 A1, 2015 ; Location in patent: Page/Page column ;

Hide Experimental Procedure

Title/Abstract Full Text Show Details

2:1-(6-Chloro-5-fluoro-1H-indol-3-yl)-propan-2-one

1-(6-Chloro-5-fluoro-1H-indol-3-yl)-propan-2-one Under N2, Pt/C (10 g, 5percent Pt on Carbon) was charged to the suspension of 6-Chloro-5-fluoro-3-((Z)-2-nitro-propenyl)-1H-indole (100 g, 0.39 mol) in ethyl acetate (500 mL). The reaction mixture vacuumed and purged with H2 three times and stirred at r.t. for overnight. The catalyst was filtered off and the organic solvent was removed under reduced pressure to give brown oil. The oil was re-dissolved in EtOH (500 mL) and sodium bisulfite (81.7 g, 0.79 mol) in H2O ( ) was added. The suspension was heated up to 80° C. for overnight. The precipitate was filtered off and ethanol was removed under pressure. The residue was diluted with water (500 mL) and extracted with ethyl acetate (300 mL*2). The combined organic layer was dried over Na2SO4 and condensed on the rota vapor to give brown oil (53 g, 60percent yield). Hide Details

With acetic acid in water

Hide Experimental Procedure

Patent: US2015/45562 A1, 2015 ; Location in patent: Page/Page column ; Title/Abstract Full Text Show Details

3:1-(6-Chloro-5-fluoro-1H-indol-3-yl)-propan-2-one

1-(6-Chloro-5-fluoro-1H-indol-3-yl)-propan-2-one Raney/Ni (0.75 g) and acetic acid (1.1 mL, 19.6 mmol) were charged to the suspension of 6-Chloro-5-fluoro-3-((Z)-2-nitro-propenyl)-1H-indole (5 g, 19.6 mmol) in the mixture of MeOH and H2O (2:1, 50 mL) at r.t. The reaction mixture vacuumed and purged with H2 three times and heated at 50° C. for overnight. MeOH (50 mL) was added to the reaction mixture and the catalyst was filtered off over celite. The solvent was concentrated to 50 mL and H2O (300 ml) was added. With the addition of H2O, off-white solid was produced. The solid was filtered and washed by water. After dried in the oven, 2.53 g off-white solid was isolated.

140

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With iron; acetic acid in methanol; water

Heating;

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Rx-ID: 27987771

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Yeates, Clive L.; Batchelor, John F.; Capon, Edward C.; Cheesman, Neil J.; Fry, Mitch; Hudson, Alan T.; Pudney, Mary; Trimming, Helen; Woolven, James; Bueno, Jose M.; Chicharro, Jesus; Fernandez, Esther; Fiandor, Jose M.; Gargallo-Viola, Domingo; De Las Heras, Federico Gomez; Herreros, Esperanza; Leon, Maria L.

Journal of Medicinal Chemistry, 2008 , vol. 51, # 9 p. 2845 - 2852 Title/Abstract Full Text View citing articles Show Details

141

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With iron; acetic acid

T=100°C; 2 h;

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Rx-ID: 28953162

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European Journal of Medicinal Chemistry, 2009 , vol. 44, # 12 p. 4862 - 4888 Title/Abstract Full Text View citing articles Show Details

142

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56%

Stage #1: With sodium tetrahydroborate in methanol

T=0 - 20°C; Nef reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol; water

T=0 - 20°C; Nef reaction; 18 h; Hide Experimental Procedure

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Rx-ID: 32091586

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Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron Letters, 2011 , vol. 52, # 49 p. 6566 - 6568 Title/Abstract Full Text View citing articles Show Details

(II) General procedure of Nef reaction.

General procedure: The nitro-alkene compound 10 (1.0 mmol) was dissolved in methanol (10 mL) and cooled to 00C. NaBH4 (2.0 mmol) was added in portion. After two hours stirring at rt, the reaction mixture was cooled to 00C. To this cold mixture, 30percent H2O2 (2.6 mL) and K2CO3 (7.9 mmol) were added and the reaction mixture was further stirred for 18h at rt. The reaction mixture was then acidified with 2N HCl (5 mL), extracted with CH2Cl2 (3 X 20 mL). The combined organic layer was washed with brine (2 X 20 mL), dried over anhy.Na2SO4 and concentrated under reduced pressure. The crude product obtained was purified by column chromatography (SiO2, hexanes / EtOAc, 8.5:1.5).

56%

Stage #1: With sodium tetrahydroborate in methanol

T=20°C; Nef Reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol

T=20°C; 18 h; Hide Experimental Procedure

Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron, 2013 , vol. 69, # 30 p. 6129 - 6143 Title/Abstract Full Text View citing articles Show Details

General procedure of Nef reaction.

General procedure: To a pre cooled solution of nitroalkene 20–22(a–c) (1.0mmol) in MeOH (10mL) was added NaBH4 (2.0mmol) in portion. After 2h stirring at rt, the reaction mixture was cooled to 0°C. To this cold mixture, 30percent H2O2 (2.6mL) and K2CO3 (7.9mmol) were added and the reaction mixture was further stirred for 18h at rt. The reaction mixture was then acidified with 2N HCl (5mL), extracted with CH2Cl2 (3×20mL). The combined organic layer was washed with brine (2×20mL), dried over anhyd Na2SO4 and concentrated under reduced pressure. The crude product obtained was purified by column chromatography (SiO2, hexane/EtOAc, 8.5:1.5).

143

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Stage #1: With sodium tetrahydroborate in methanol

T=20°C; Nef Reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol

T=20°C; 18 h; Hide Experimental Procedure

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Rx-ID: 35934298

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Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron, 2013 , vol. 69, # 30 p. 6129 - 6143 Title/Abstract Full Text View citing articles Show Details

4.3.35 Ethyl (2R)-2-(2-oxobutyl)piperidine-1-carboxylate (19c).

General procedure: General procedure of Nef reactionTo a pre cooled solution of nitroalkene 20–22(a–c) (1.0 mmol) in MeOH (10 mL) was added NaBH4 (2.0 mmol) in portion. After 2 h stirring at rt, the reaction mixture was cooled to 0°C. To this cold mixture, 30percent H2O2 (2.6 mL) and K2CO3 (7.9 mmol) were added and the reaction mixture was further stirred for 18 h at rt.

144

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Rx-ID: 21296116

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Davey, D. D.; Lumma, W. C.

Journal of Organic Chemistry, 1989 , vol. 54, # 13 p. 3211 - 3213 Title/Abstract Full Text View citing articles Show Details

145

Synthesize Find similar With hydrogenchloride; iron in tetrahydrofuran; water

T=60 - 100°C; 21 h; Hide Experimental Procedure

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Rx-ID: 23324286

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NOVARTIS AG; NOVARTIS PHARMA GMBH

Patent: WO2005/21519 A2, 2005 ; Location in patent: Page/Page column 25 ;

Title/Abstract Full Text Show Details

AA3:

Iron powder (25 g, 0.45 mol) is added to a stirred mixture of freshly prepared 2-FLUORO-1- METHANESULFONYL-4- (2-NITRO-PROPENYL)-BENZENE (Example AA2) (29 g, 0.112 mol) in THF (50 ml). Water (110 ml) is added and the mixture is heated to 60° C. Concentrated hydrochloric acid (50 ml) is added slowly over 1H at 6090° C. The reaction is then stirred at 100° C for 20 hours then diluted with cold water (500 ml) and filtered through CeliteTM filter material washing with chloroform (500 ml). he organic extract is washed with water (200 ml) followed by brine (200 ml). After drying (MGS04) the mixture is absorbed on silica and purified by chromatography, eluting with hexane-ethyl acetate (1: 1) to give the titled compound.

With hydrogenchloride; iron in tetrahydrofuran; water

T=60 - 100°C; 21 h; Hide Experimental Procedure

NOVARTIS AG; NOVARTIS PHARMA GMBH

Patent: WO2007/134827 A1, 2007 ; Location in patent: Page/Page column 28-29 ; Title/Abstract Full Text Show Details

AA3:

Iron powder (25 g, 0.45 mol) was added to a stirred mixture of freshly prepared 2-fluoro-l- methanesulfonyl-4-(2-nitro-propenyl)-benzene (Example AA2) (29 g, 0.112 mol) in THF (50 ml). Water (110 ml) was added and the mixture is heated to 60° C. Concentrated hydrochloric acid (50 ml) was added slowly over Ih at 60-90° C. The reaction was then stirred at 100° C for 20 hours then diluted with cold water (500 ml) and filtered through Celite.(TM). filter material washing with chloroform (500 ml). The organic extract was washed with water (200 ml)

Stage #1: With water; iron in tetrahydrofuran

T=60°C; Stage #2: With hydrogenchloride; water in tetrahydrofuran

T=60 - 100°C; 21 h; Hide Experimental Procedure

NOVARTIS AG; NOVARTIS PHARMA GMBH

Patent: WO2003/72557 A1, 2003 ; Location in patent: Page/Page column 52 ; Title/Abstract Full Text Show Details

64.c:

Iron powder (25 g, 0.45 mol) is added to a stirred mixture of freshly prepared 2-fluoro-1- methanesulfonyl-4- (2-nitro-propenyl)-benzene (Example 64b) (29 g, 0.112 mol) in THF (50 ml). Water (110 ml) is added and the mixture is heated to 60°C. Concentrated hydrochloric acid (50 ml) is added slowly over 1h at 60-90° C. The reaction is then stirred at 100° C for 20 hours then diluted with cold water (500 ml) and filtered through celiteTM filter material washing with chloroform (500 ml). The organic extract is washed with water (200 ml) followed by brine (200 ml). After drying (MgS04 the mixture is absorbed on silica and purified by chromatography, eluting with hexane-ethyl acetate (1: 1) to give the title compound. Hide Details

With iron; acetic acid

T=60 - 100°C; 2 h; Hide Experimental Procedure

NOVARTIS AG; NOVARTIS PHARMA GMBH

Patent: WO2004/78754 A1, 2004 ; Location in patent: Page 52 ; Title/Abstract Full Text Show Details

68.c:68c) 1-(3-Fluoro-4-methanesulfonyl-phenyl)-propan-2-one

Freshly prepared 2-FLUORO-1-METHANESULFONYL-4- (2-NITRO-PROPENYL)-BENZENE (Example 68b) (20 g, 77 mmol) in glacial acetic acid (150 ml) is added slowly in 15 x 10ML portions to a stirred slurry of iron powder (46 g, 833 mmol) in glacial acetic acid (150 ml) at 60°C. The reaction mixture is heated at 100 C for an additional 2 hours, allowed to cool to room temperature and poured on to ice water (600 ml). The mixture is filtered through celite to remove iron residues, washing with dichloromethane (300 ml). The organic layer is removed and the aqueous solution is extracted with more DCM (3 x 200 ml). The combined organic extracts are dried (MGS04), filtered and concentrated to a red solution. The titled product crystallises from this solution on standing.

With iron; acetic acid

T=100°C;

Bioorganic and Medicinal Chemistry Letters, 2012 , vol. 22, # 17 p. 5445 - 5450 Title/Abstract Full Text View citing articles Show Details

With iron; acetic acid

T=100°C; 2 h;

Hirt, Hans; Haenggi, Ruedi; Reyes, Jesus; Seeger-Weibel, Manuela; Gallou, Fabrice

Organic Process Research and Development, 2008 , vol. 12, # 1 p. 111 - 115 Title/Abstract Full Text View citing articles Show Details

146

Rx-ID: 25340385

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60.5%

With hydrogenchloride; iron(III) chloride in diethyl ether

Synthelabo

Patent: US4129598 A1, 1978 ;

Hide Experimental Procedure

Title/Abstract Full Text Show Details

1.c:(c)

(c) 1-(3'-Trifluoromethylthio-phenyl)-2-propanone 13.2 g (50 mmols) of 1-(3'-trifluoromethylthio-phenyl)-2-nitro-propene, 19.6 g (0.35g atom) of iron powder and 0.25 g of ferric chloride are introduced into a 250 ml three-necked flask equipped with a mechanical stirrer, a condenser and a dropping funnel and this mixture is heated on an oil bath at 80°-90° C. 13.5 ml of concentrated hydrochloric acid are added dropwise, via the dropping funnel, with stirring, over the course of 7 hours, while the temperature is kept at 90° C. The reaction mixture is allowed to cool and rendered alkaline with sodium hydroxide solution. The ketone is then steam distilled. The distillate is extracted twice in succession with 100 ml. of diethyl ether each time. The two ether extracts are combined, dried over sodium sulphate and filtered. The solvent is evaporated from the filtrate in vacuo on a water bath, and the residue is rectified. 7.1g (60.5 percent yield) of 1-(3'-trifluoromethylthio-phenyl)-2-propanone are thus obtained as a colourless oil, b.p. 138°-146° C/25-30 mm.Hg, nD23° = 1.489.

147

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89%

With chromium dichloride; hydrogenchloride; water in tetrahydrofuran

T=20°C; 16 h; Hide Experimental Procedure

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Rx-ID: 27770368

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Betschart, Claudia; Lerchner, Andreas; Machauer, Rainer; Rueger, Heinrich; Tintelnot-Blomley, Marina; Veenstra, Siem Jacob

Patent: US2008/132477 A1, 2008 ; Location in patent: Page/Page column 40 ; Title/Abstract Full Text Show Details

A40.d:

CrCl2 (1.77 g, 14.4 mmol, 10 eq) is suspended in 1N HCl in H2O (10 ml), and 3-allyloxy-5-((E)-2-nitro-propenyl)-benzoic acid (400 mg, 1.44 mmol, 1 eq) is added as solution in THF (10 ml). The reaction mixture is stirred for 16 h at room temperature. The mixture is then diluted with 50 ml of Et2O, the organic layer is separated and washed with brine, dried over sodiumsulfate, filtered and concentrated to give the product (300 mg, 89percent).MS (ES+): 252=[M+NH4]+ 1H-NMR (400 MHz, CDCl3): 7.60-7.58 (m, 2H), 7.06 (dd, 1H), 6.15-6.02 (m, 1H), 5.50-5.33 (m, 2H), 4.62 (d, 2H), 3.79 (s, 2H), 2.22 (s, 3H).

148

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With iron; acetic acid

T=100°C;

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Rx-ID: 33838022

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Bioorganic and Medicinal Chemistry Letters, 2012 , vol. 22, # 17 p. 5445 - 5450 Title/Abstract Full Text View citing articles Show Details

149

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A: 23% B: 68%

With ammonium formate; palladium on activated charcoal in tetrahydrofuran; methanol

0.5 h; Ambient temperature;

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Kabalka, George W.; Pace, R. David; Wadgaonkar, P.P.

Synthetic Communications, 1990 , vol. 20, # 16 p. 2453 - 2458 Title/Abstract Full Text Show Details

150

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83.3%

With hydrogenchloride; iron in methanol; water

T=20 - 70°C; 3 h; Inert atmosphere; Hide Experimental Procedure

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Rx-ID: 29441441

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SYNGENTA PARTICIPATIONS AG; RAJAN, Ramya; WALTER, Harald; STIERLI, Daniel

Patent: WO2010/63700 A2, 2010 ; Location in patent: Page/Page column 34; 52 ; Title/Abstract Full Text Show Details

P15.b; P.28:

b) Preparation of 1-(2,4,6-trichloro-phenyl)-propan-2-one:To a stirred solution of above obtained nitrostyrene (5g, 18.72 mmol) in water (20 ml) and methanol (60 ml), was added Iron powder (2.355 gms , 42.12 mmol) followed by cone. HCI (1 1.5 ml, 1 12 mmol) at ambient under nitrogen atmosphere. The reaction mixture was stirred at 700C for 1 hour. After 1 hour, the remaining quantity of iron powder (2.355 gms , 42.12 mmol) and cone. HCI (1 1.5 ml, 1 12 mmol) was added to this reaction mass and stirring continued for 2 hours at 700C. When TLC confirmed the completion of the reaction, reaction mass was cooled to ambient temperature and methanol was removed with a rotavapor. The resulting residue was then diluted with water and extracted with ethyl acetate (3x 80 ml). The combined ethyl acetate layer was finally washed with water, followed by brine wash and dried under anhydrous sodium sulfate before the complete evaporation of solvents. The resulting crude mass was purified by column chromatography using 60-120 μ mesh silica gel and product collected at 5percent ethyl acetate in hexane as elution system to give 1-(2,4,6-trichloro-phenyl)-propan-2-one (3.7 g, 83.3percent). 1H NMR (400MHz, CDCI3): δ 2.26 (s,3H,CH3 ), 4.05(s,2H,CH2), 7.34 (s,2H, Ar-H); Example P28: Preparation of 1-(2,4,6-trichloro-phenyl)-propan-2-one:To the stirred solution of 1 ,3,5-trichloro-2-((E)-2-nitro-propenyl)-benzene (5g, 18.72 mmol) in H2O (20 ml) and MeOH (60 ml), iron powder (2.355 g , 42.12 mmoles) and cone. HCI (1 1.5 ml, 1 12 mmol) was added at ambient temperature under nitrogen environment. The reaction mixture was stirred at 700C for 1 hour. After 1 hour additional iron powder (2.355 g , 42.12 mmoles) and cone. HCI (1 1.5 ml, 1 12 mmol) was added, while stirring was continued for 2 hours at 700C. After completion of the reaction, (confirmed by TLC) reaction mass was cooled to ambient temperature and MeOH was evaporated. The resulting residue was diluted with water and extracted with ethyl acetate (3x 80 ml). Combined ethyl acetate layer was washed with water and brine and dried over anhydrous Na2SO4. The organic layer was concentrated under vacuum. The crude material was purified by column chromatography (silicagel 60-120 μ mesh, hexane/ethylacetate 95:5) to afford 3.7g (83.3percent of theory) of 1- (2,4,6-Trichloro-phenyl)-propan-2-one.

151

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83.3%

With hydrogenchloride; water in methanol

T=70°C; 3 h; Hide Experimental Procedure

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SYNGENTA CROP PROTECTION LLC

Patent: US2011/230537 A1, 2011 ; Location in patent: Page/Page column 15; 23 ; Title/Abstract Full Text Show Details

P15.b; P28:

To a stirred solution of above obtained nitrostyrene (5 g, 18.72 mmol) in water (20 ml) and methanol (60 ml), was added Iron powder (2.355 gms, 42.12 mmol) followed by conc. HCl (11.5 ml, 112 mmol) at ambient under nitrogen atmosphere. The reaction mixture was stirred at 70° C. for 1 hour. After 1 hour, the remaining quantity of iron powder (2.355 gms, 42.12 mmol) and conc. HCl (11.5 ml, 112 mmol) was added to this reaction mass and stirring continued for 2 hours at 70° C. When TLC confirmed the completion of the reaction, reaction mass was cooled to ambient temperature and methanol was removed with a rotavapor. The resulting residue was then diluted with water and extracted with ethyl acetate (3*80 ml). The combined ethyl acetate layer was finally washed with water, followed by brine wash and dried under anhydrous sodium sulfate before the complete evaporation of solvents. The resulting crude mass was purified by column chromatography using 60-120μmesh silica gel and product collected at 5percent ethyl acetate in hexane as elution system to give 1-(2,4,6-trichloro-phenyl)-propan-2-one (3.7 g, 83.3percent). 1H NMR (400 MHz, CDCl ): δ 2.26 (s, 3H, CH ), 4.05 (s, 2H, CH ), 7.34 (s, 2H, Ar-H) 3 3 2

152

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Multi-step reaction with 2 steps 1: H2 / Pd-C / ethanol 2: aq. HNO3, NaNO2 / acetic acid View Scheme

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Rx-ID: 22727903

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Coutts; Malicky

Canadian Journal of Chemistry, 1973 , vol. 51, # 9 p. 1402 - 1409 Title/Abstract Full Text View citing articles Show Details

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153

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B: 87%

With indium; chloro-trimethyl-silane

T=25°C; Reduction; Addition; 3.5 h;

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Yadav; Subba Reddy; Srinivas; Ramalingam

Synlett, 2000 , # 10 p. 1447 - 1449 Title/Abstract Full Text View citing articles Show Details

154

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Multi-step reaction with 3 steps 1: 100 percent / sodium borohydride / propan-2-ol; tetrahydrofuran / 24 h / Ambient temperature 2: diphenyl disulphide, tributylphosphine / tetrahydrofuran / 3 h / Ambient temperature 3: water / tetrahydrofuran / Ambient temperature View Scheme

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Rx-ID: 20689166

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Barton, Derek H. R.; Motherwell, William B.; Simon, Ethan S.; Zard, Samir Z.

Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1986 , p. 2243 - 2252 Title/Abstract Full Text View citing articles Show Details

155

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Multi-step reaction with 2 steps 1: 88 percent / AcOH, Fe / Heating 2: 69 percent / 35percent H2O2 / methanol / 0.67 h / 60 °C View Scheme

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Rx-ID: 19169130

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Jacob III; Shulgin

Journal of Medicinal Chemistry, 1983 , vol. 26, # 5 p. 746 - 752 Title/Abstract Full Text View citing articles Show Details

156

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60%

Stage #1: With sodium tetrahydroborate in methanol

T=20°C; Nef Reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol

T=20°C; 18 h; Hide Experimental Procedure

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Rx-ID: 35934208

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Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron, 2013 , vol. 69, # 30 p. 6129 - 6143 Title/Abstract Full Text View citing articles Show Details

4.3.17 tert-Butyl (2S)-2-(2-oxopropyl)piperidine-1-carboxylate (18b).

General procedure: Following the general procedure II, compound 21b (0.25g, 1.0mmol) on Nef reaction gave 18b (0.15g, 60percent) as a thick yellow liquid.

157

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89.6%

With hydrogenchloride; sodium phosphite; nickel in ethanol; water

T=60°C; 2 h;

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Rx-ID: 3579491

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Strasser; Cooper; Dewald; Payne

Helvetica Chimica Acta, 1988 , vol. 71, # 5 p. 1156 - 1176 Title/Abstract Full Text View citing articles Show Details

158

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33%

With hydrogenchloride; anhydrous iron chloride; iron in toluene

T=75°C; 3 h; Hide Experimental Procedure

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Rx-ID: 22885413

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Fujisawa Pharmaceutical Co., Ltd.

Patent: US6348474 B1, 2002 ; Location in patent: Page column 65 ; Title/Abstract Full Text Show Details

29.2:Preparation Example 29-2 (5-Bromo-2-methoxyphenyl)acetone

The oil was dissolved in toluene (30 ml) and an aqueous solution (30 ml) of iron(III) chloride hexahydrate (1.0 g) was added.. Thereto was added iron powder (15.1 g, 270 mmol) and the mixture was heated to 75° C. While vigorously stirring the mixture, concentrated hydrochloric acid (37.5 ml, 450 mmol) was dropwise added over 2 hr.. After the dropwise addition, the mixture was stirred for 1 hr at 75° C. After cooling, the insoluble matter was filtered off and the filtrate was partitioned.. The aqueous layer was extracted with toluene.. The organic layers were combined, washed with 3N hydrochloric acid, and dried over anhydrous sodium sulfate.. The desiccant was filtered off and the filtrate was concentrated under reduced pressure.. The residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=4/1) to give the objective compound (6.9 g, 33percent) as a colorless oil. 1H-NMR(CDCl3, δ ppm): 7.36(1H, dd, J=2.4 and 8.7 Hz), 7.24(1H, d, J=2.4 Hz), 6.75(1H, d, J=9.0 Hz), 3.78(3H, s), 3.63(2H, s), 2.15(3H, s)

159

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Rx-ID: 24282529

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With hydrogenchloride; iron(III) chloride in hexane; dichloromethane; water; ethyl acetate; toluene

Merck and Co., Inc.

Patent: US5877191 A1, 1999 ;

Hide Experimental Procedure

Title/Abstract Full Text Show Details

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227.A:Step A

Step A 1-(3-Bromo-4-methoxyphenyl)acetone A solution of 790 mg (2.90 mmol) of 1-(3-bromo-4-methoxyphenyl)-2-nitropropene (from Example 80, Step A) in 5.0 mL of toluene was combined with water (2.0 mL), iron powder (730 mg, 13.45 mmol), and ferric chloride (14.2 mg, 0.088 mmol) in a 25-mL three-neck round bottom flask fitted with a mechanical stirrer and reflux condenser. With vigorous agitation, the suspension was heated at 80° C., and 1.3 mL of conc. HCl was added over a period of 2 h via syringe. After the addition was completed, the heating and stirring were continued for an additional 30 min. After the reaction had cooled to RT, ethyl acetate (50 mL) was added to the solid was removed by filtration. The filtrate was washed with 20 mL of saturated aqueous sodium bicarbonate and the layers were separated. The aqueous layer was filtered again and the filtrate was extracted with 2*40 mL of ethyl acetate. The combined ethyl acetate extracts were washed with 50 mL of brine. Drying over sodium sulfate and concentration afforded a red oil which was purified by flash column chromatography, eluding with 30percent dichloromethane in hexane followed by dichloromethane, to give 411 mg of the title compound as a yellow syrup.

160

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With iron; acetic acid in methanol; water

Heating;

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Rx-ID: 27987775

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Journal of Medicinal Chemistry, 2008 , vol. 51, # 9 p. 2845 - 2852 Title/Abstract Full Text View citing articles Show Details

161

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86%

Stage #1: With anhydrous iron chloride; iron in toluene Nef Reaction; 0.25 h; Stage #2: With hydrogenchloride in water

Nef Reaction; 0.5 h; Hide Experimental Procedure

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Rx-ID: 38199485

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Limaye, Rohan A.; Natu, Arun D.; Paradkar, Madhusudan V.

Synthetic Communications, 2014 , vol. 44, # 17 p. 2503 - 2509 Title/Abstract Full Text View citing articles Show Details

Preparation of 1-(1,4-Dimethoxynaphthalen-2yl)propan-2-one (9)

Iron powder (2 g, 0.035 mol) and ferric chloride (pinch) were added to asolution of 1,4-dimethoxy-2-(E-2-nitroprop-1-enyl) naphthalene (8, 2 g, 0.007 mol) in toluene (20 ml). The mixture was stirred at 70° C for 15 min, followed by dropwise addition of concentrated HCl (20 ml). The reaction was continued for 30 min and worked

up in the usual manner. The crude mass thus obtained was purified by column chromatography over silica gel using hexane–ethyl acetate (8:2) as eluent that yielded 1-(1,4-dimethoxynaphthalen-3-yl)propan-2-one (9) as a colorless oil. Yield: 1.48 g (86percent)

162

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50%

With hydrogenchloride; iron(III) chloride; iron in water; toluene

T=80°C; 15 h;

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Rx-ID: 2583454

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Monge Vega; Martinez; Palop; et al.

Journal of Heterocyclic Chemistry, 1981 , vol. 18, # 5 p. 889 - 892 Title/Abstract Full Text View citing articles Show Details

163

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With iron; acetic acid

T=100°C;

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Rx-ID: 33838005

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Bioorganic and Medicinal Chemistry Letters, 2012 , vol. 22, # 17 p. 5445 - 5450 Title/Abstract Full Text View citing articles Show Details

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164

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A: 32% B: 60%

With titanium(III) chloride in tetrahydrofuran; water

T=35°C; 24 h; pH 6.5;

Sera, Akira; Fukumoto, Shoji; Tamura, Masako; Takabatake, Kiyoshi; Yamada, Hiroaki; Itoh, Kuniaki

Bulletin of the Chemical Society of Japan, 1991 , vol. 64, # 6 p. 1787 - 1791 Title/Abstract Full Text Show Details

A: 32%

With titanium(III) chloride; ammonium acetate in

Sera, Akira; Fukumoto, Shoji; Yoneda, Takako; Yamada, Hiroaki

B: 60%

tetrahydrofuran; water

T=35°C; 24 h;

Heterocycles, 1986 , vol. 24, # 3 p. 697 - 702 Title/Abstract Full Text View citing articles Show Details

A: 32% B: 60%

With titanium(III) chloride in n-heptane

T=35°C; 24 h; other 1-nitro-2-phenylethenes;

Sera, Akira; Fukumoto, Shoji; Tamura, Masako; Takabatake, Kiyoshi; Yamada, Hiroaki; Itoh, Kuniaki

Bulletin of the Chemical Society of Japan, 1991 , vol. 64, # 6 p. 1787 - 1791 Title/Abstract Full Text Show Details

Hide Details

A: 32% B: 60%

With titanium(III) chloride; ammonium acetate in tetrahydrofuran; water

T=35°C; 24 h;

Sera, Akira; Fukumoto, Shoji; Yoneda, Takako; Yamada, Hiroaki

Heterocycles, 1986 , vol. 24, # 3 p. 697 - 702 Title/Abstract Full Text View citing articles Show Details

A: 32% B: 60%

With titanium(III) chloride in tetrahydrofuran; water

T=35°C; 24 h; pH 6.5;

Sera, Akira; Fukumoto, Shoji; Tamura, Masako; Takabatake, Kiyoshi; Yamada, Hiroaki; Itoh, Kuniaki

Bulletin of the Chemical Society of Japan, 1991 , vol. 64, # 6 p. 1787 - 1791 Title/Abstract Full Text Show Details

165

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70%

With hydrogenchloride; iron(III) chloride; iron in methanol; water

4 h; Heating;

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Rx-ID: 3262319

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Sircar; Duell; Bristol; Weishaar; Evans

Journal of Medicinal Chemistry, 1987 , vol. 30, # 6 p. 1023 - 1029 Title/Abstract Full Text View citing articles Show Details

166

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85%

With hydrogenchloride; iron in ethanol

7 h; Heating;

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Rx-ID: 3073612

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Montanari; Chiarini; Budriesi; Valenti

Journal of Heterocyclic Chemistry, 1992 , vol. 29, # 1 p. 259 - 261 Title/Abstract Full Text View citing articles Show Details

167

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55%

With hydrogenchloride; iron in ethanol

7 h; Heating;

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Rx-ID: 3073619

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Montanari; Chiarini; Budriesi; Valenti

Journal of Heterocyclic Chemistry, 1992 , vol. 29, # 1 p. 259 - 261 Title/Abstract Full Text View citing articles Show Details

168

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62%

With hydrogenchloride; iron in ethanol

7 h; Heating;

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Rx-ID: 3073631

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Montanari; Chiarini; Budriesi; Valenti

Journal of Heterocyclic Chemistry, 1992 , vol. 29, # 1 p. 259 - 261 Title/Abstract Full Text View citing articles Show Details

169

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63%

With hydrogenchloride; iron in ethanol

7 h; Heating;

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Rx-ID: 3073638

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Montanari; Chiarini; Budriesi; Valenti

Journal of Heterocyclic Chemistry, 1992 , vol. 29, # 1 p. 259 - 261 Title/Abstract Full Text View citing articles Show Details

170

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Rx-ID: 2583403

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86%

With sodium hypophosphite; nickel in ethanol; water

T=40 - 60°C; 2 h;

Monti, Diego; Gramatica, Paola; Speranza, Giovanna; Manitto, Paolo

Tetrahedron Letters, 1983 , vol. 24, # 4 p. 417 - 418 Title/Abstract Full Text View citing articles Show Details

85.6%

With sodium hypophosphite; nickel in hydrogenchloride; ethanol; water

T=60°C; 3 h;

Monti; Gramatica; Manitto

Farmaco, Edizione Scientifica, 1981 , vol. 36, # 6 p. 412 - 418 Title/Abstract Full Text View citing articles Show Details

171

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50%

With hydrogenchloride; iron(III) chloride; iron in methanol; water

4 h; Heating;

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Rx-ID: 3266476

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Sircar; Duell; Bristol; Weishaar; Evans

Journal of Medicinal Chemistry, 1987 , vol. 30, # 6 p. 1023 - 1029 Title/Abstract Full Text View citing articles Show Details

172

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With sulfuric acid; L-Selectridereg;

Multistep reaction;

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Rx-ID: 4842692

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Shih, Neng-Yang; Aslanian, Robert; Lupo Jr., Andrew T.; Orlando, Steve; Piwinski, John J.; Green, Michael J.; Ganguly, Ashit K.; West, Robert; Tozzi, Salvatore; Kreutner, William; Hey, John A.

Bioorganic and Medicinal Chemistry Letters, 1998 , vol. 8, # 3 p. 243 - 248 Title/Abstract Full Text View citing articles Show Details

173

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70%

Stage #1: With sodium tetrahydroborate in methanol

T=20°C; Nef Reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol

T=20°C; 18 h; Hide Experimental Procedure

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Rx-ID: 35934296

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Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron, 2013 , vol. 69, # 30 p. 6129 - 6143 Title/Abstract Full Text View citing articles Show Details

4.3.33 Benzyl (2R)-2-(2-oxobutyl)piperidine-1-carboxylate (19a).

174

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80%

With hydrogenchloride; iron(III) chloride; iron in water

Hide Experimental Procedure

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Rx-ID: 24355095

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Banyu Pharmaceutical Co., Ltd.

Patent: US6011174 A1, 2000 ; Title/Abstract Full Text Show Details

54.3:(3)

(3) Preparation of 3-methoxy-4-phenoxyphenylacetone 953 mg of 1-(3-methoxy-4-phenoxyphenyl)-2-nitropropene, 1.31 g of iron, 9.5 mg of ferric chloride and 5 ml of water were mixed, and 1.5 ml of 6N hydrochloric acid was dropwise added over a period of 1.5 hours under reflux and heating. The reaction solution was subjected to celite filtration, and the filtrate was extracted with ethyl acetate. The extract solution was washed with a saturated sodium hydrogen carbonate aqueous solution and then, dried over anhydrous sodium sulfate. The drying agent was filtered off, and then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=10/1) to obtain 688 mg (yield: 80percent) of the above identified compound as a colorless oily substance.

175

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50%

With hydrogenchloride; iron(III) chloride; iron in water; toluene

T=80°C; 15 h;

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Rx-ID: 2594882

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Monge Vega; Martinez; Palop; et al.

Journal of Heterocyclic Chemistry, 1981 , vol. 18, # 5 p. 889 - 892 Title/Abstract Full Text View citing articles Show Details

176

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Rx-ID: 1062277

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With hydrogenchloride; iron(III) chloride; iron

1 h; Heating;

Binovic,K.; Vrancea,S.

Chimica Therapeutica, 1968 , vol. 3, p. 313 - 320 Full Text View citing articles Show Details

Stage #1: With acetic acid; iron

T=60 - 100°C; Stage #2: With water

NOVARTIS AG

Patent: WO2008/52733 A1, 2008 ; Location in patent: Page/Page column 63; 64 ;

Hide Experimental Procedure

Title/Abstract Full Text Show Details

10.2:

A mixture of 3 g (12.8 mmol) of 4-iodobenzaldehyde (Pfaltz-Bauer) and 302 mg (3.88 mmol) of ammonium acetate in 7.51 ml of nitroethane is stirred under argon for 15 h at 125°C. The reaction mixture is then concentrated under reduced pressure. The residue is dissolved in CH2CI2 and the organic phase washed with water and brine. After drying (Na2SO4), the solvent is evaporated and the residue is solubilized in a few ml of glacial acetic acid. This solution is added slowly to a slurry of 2.9 g (51.7 mmol) of iron powder in 8 ml of glacial acetic acid at 600C. The reaction is stirred overnight at 100°C. The cold reaction mixture is poured into ice water. The brown suspension is filtered over hyflo and the residue on the filter is washed with ample CH2CI2. The filtered phase is separated off, the organic phase is washed successively with 1 M hydrochloric acid, sat. NaHCO3 solution, water and brine. After drying EPO <DP n="65"/>over MgSO4, the solvent is evaporated and the residue purified by flash chromatography. Solvent system: hexane-ethylacetate = 90:10. HPLC; tR = 6.14 min.

177

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With hydrogenchloride; iron(III) chloride; iron

1 h; Heating;

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Rx-ID: 1062904

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Binovic,K.; Vrancea,S.

Chimica Therapeutica, 1968 , vol. 3, p. 313 - 320 Full Text View citing articles Show Details

178

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With hydrogenchloride; iron(III) chloride; iron

1 h; Heating;

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Rx-ID: 1063061

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Binovic,K.; Vrancea,S.

Chimica Therapeutica, 1968 , vol. 3, p. 313 - 320 Full Text View citing articles Show Details

179

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65%

With iron; acetic acid in methanol; water

3 h; Heating;

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Rx-ID: 27987779

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Journal of Medicinal Chemistry, 2008 , vol. 51, # 9 p. 2845 - 2852 Title/Abstract Full Text View citing articles Show Details

180

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65%

With iron; acetic acid in methanol; water

Heating;

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Rx-ID: 27987783

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Journal of Medicinal Chemistry, 2008 , vol. 51, # 9 p. 2845 - 2852 Title/Abstract Full Text View citing articles Show Details

181

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Rx-ID: 24278145

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With hydrogenchloride; iron(III) chloride in water; ethyl acetate; toluene

Nippon Soda Co., Ltd.

Patent: US5948917 A1, 1999 ;

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Title/Abstract Full Text Show Details

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R.5:Production of methyl 2,4-dichloro-3-(2-oxopropyl) benzoate STR27

Referential Example 5 Production of methyl 2,4-dichloro-3-(2-oxopropyl) benzoate STR27 A solution of 25.72 g of methyl 2,4-dichloro-3-formyl benzoate in 100 ml of toluene and 39.0 g of nitroethane and 1.5 g of n-butyl amine added thereto were refluxed together for 21 hours. The reaction solution was poured into ice, extracted from ethyl acetate, washed with 1-N hydrochloric acid, then with saturated saline solution, and dried over magnesium sulfate. The solution was distilled under a reduced pressure to expel the solvent and obtain 34.9 g of methyl 2,4-dichloro-3-(2-nitro-1-propenyl) benzoate. A solution of 30.1 g of the benzoate so obtained in a mixed solvent consisting of 120 ml of toluene and 360 ml of water was mixed with 20.8 g of iron powder and 0.4 g of ferric chloride. To the mixture, 104 g of concentrated hydrochloric acid was added dropwise at 80° C. After the dropwise addition was completed, the resultant mixture was further left reacting as refluxed for one hour. The reaction solution was cooled, mixed with ethyl acetate, and filtered to separate an insoluble portion. The organic layer was washed with water, then with saturated saline solution, and dried over magnesium sulfate. The solution was distilled under a reduced pressure to expel the solvent. When the residue was refined by silica gel chromatography, 19.53 g of methyl 2,4-dichloro-3-(2-oxopropyl) benzoate was obtained. nD22 1.5537.

182

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65%

Stage #1: With sodium tetrahydroborate in methanol

T=0 - 20°C; Nef reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol; water

T=0 - 20°C; Nef reaction; 18 h; Hide Experimental Procedure

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Rx-ID: 32091583

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Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron Letters, 2011 , vol. 52, # 49 p. 6566 - 6568 Title/Abstract Full Text View citing articles Show Details

(II) General procedure of Nef reaction.

65%

Stage #1: With sodium tetrahydroborate in methanol

T=20°C; Nef Reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol

T=20°C; 18 h; Hide Experimental Procedure

Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron, 2013 , vol. 69, # 30 p. 6129 - 6143 Title/Abstract Full Text View citing articles Show Details

General procedure of Nef reaction.

183

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95%

With hydrogenchloride; iron(III) chloride in water

6 h; Heating;

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Rx-ID: 9037373

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Pizarro, Nieves; De la Torre, Rafael; Farre, Magi; Segura, Jordi; Llebaria, Amadeu; Joglar, Jesus

Bioorganic and Medicinal Chemistry, 2002 , vol. 10, # 4 p. 1085 - 1092 Title/Abstract Full Text View citing articles Show Details

184

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Hide Experimental Procedure

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Rx-ID: 24283708

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Merck and Co., Inc.

Patent: US5877191 A1, 1999 ; Title/Abstract Full Text Show Details

228.C:Step C

Step C 1-(3-Bromo-4-isopropoxyphenyl)acetone The title compound was prepared according to the procedure of Example 227, Step A, replacing 1-(3-bromo-4-methoxyphenyl)-2-nitropropene with 1-(4-isopropoxy-3-bromophenyl)-2-nitro-1-propene.

185

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Rx-ID: 42314903

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99%

Stage #1: With iron; acetic acid

T=60 - 100°C; 3.33333 h; Stage #2: With sodium hydroxide in water

Frichert, Alex; Jones, Peter G.; Lindel, Thomas

Angewandte Chemie - International Edition, 2016 , vol. 55, # 8 p. 2916 - 2919 Angew. Chem., 2016 , vol. 128, # 8 p. 2969 - 2972,4 Title/Abstract Full Text View citing articles Show Details

186

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Rx-ID: 25110831

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With iron(III) chloride in ethanol; water; isopropyl alcohol

Ciba-Geigy Corporation

Patent: US4329367 A1, 1982 ;

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Title/Abstract Full Text Show Details

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5:EXAMPLE 5

The starting material is prepared as follows: The mixture of 30.4 g of 1-[4-(4-chlorobenzyloxy)-phenyl]-2-nitropropene (Example 2), 80 g of iron powder, 3.2 g of ferric chloride, 40 ml of concentrated hydrochloride acid, 400 ml of ethanol and 1.2 lt of water is stirred vigorously at refux for ten hours, cooled and filtered. The residue is washed with methanol, the filtrate evaporated and the residue dissolved in hot isopropanol. The solution is treated with charcoal, filtered, the filtrate refrigerated, the precipitate collected, washed with petroleum ether and dried, to afford the 4-(4-chlorobenzyloxy)-phenylacetone melting at 76°-80°.

187

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40%

188

With hydrogenchloride; iron(III) chloride; iron in methanol; water

4 h; Heating;

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Rx-ID: 3264393

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Sircar; Duell; Bristol; Weishaar; Evans

Journal of Medicinal Chemistry, 1987 , vol. 30, # 6 p. 1023 - 1029 Title/Abstract Full Text View citing articles Show Details

Synthesize Find similar

65%

Stage #1: With sodium tetrahydroborate in methanol

T=20°C; Nef Reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol

T=20°C; 18 h; Hide Experimental Procedure

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Rx-ID: 35934182

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Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron, 2013 , vol. 69, # 30 p. 6129 - 6143 Title/Abstract Full Text View citing articles Show Details

4.3.16 Benzyl (2S)-2-(2-oxopropyl)piperidine-1-carboxylate (18a)

General procedure: Following the general procedure II, Nef reaction on 21a (0.29 g, 1.0 mmol) gave 18a (0.18 g, 65percent) as a thick liquid. A

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189

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A: 61% B: 31%

With titanium(III) chloride in tetrahydrofuran; water

T=35°C; 24 h; pH 6.5;

Sera, Akira; Fukumoto, Shoji; Tamura, Masako; Takabatake, Kiyoshi; Yamada, Hiroaki; Itoh, Kuniaki

Bulletin of the Chemical Society of Japan, 1991 , vol. 64, # 6 p. 1787 - 1791 Title/Abstract Full Text Show Details

A: 61% B: 31%

With titanium(III) chloride in tetrahydrofuran; water

T=0°C; 24 h; pH 6.5;

Sera, Akira; Fukumoto, Shoji; Tamura, Masako; Takabatake, Kiyoshi; Yamada, Hiroaki; Itoh, Kuniaki

Bulletin of the Chemical Society of Japan, 1991 , vol. 64, # 6 p. 1787 - 1791 Title/Abstract Full Text Show Details

190

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88%

With oxygen; copper dichloride; palladium dichloride in tetrahydrofuran; methanol

T=25°C; Wacker Oxidation; 12 h; Inert atmosphere; Hide Experimental Procedure

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Rx-ID: 41592834

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Chan, Chieh-Kai; Chan, Yi-Ling; Chang, Meng-Yang

Tetrahedron, 2016 , vol. 72, # 4 p. 547 - 554 Title/Abstract Full Text View citing articles Show Details

4.3 A representative synthetic procedure of skeleton 5 is as follows

General procedure: PdCl2 (13 mg, 6.5 molpercent) and CuCl2 (200 mg, 1.5 mmol) were added to a solution of skeleton 4 (1.0 mmol) in co-solvent of THF and methanol (20 mL, v/v=9:1) at 25 °C. Then oxygen was bubbled into the mixture for 3 h, and stirred at 25 °C for 10 h. The residue was diluted with water (10 mL) and the mixture was extracted with EtOAc (3×20 mL). The combined organic layers were washed with brine, dried, filtered and evaporated to afford crude product. Purification on silica gel (hexanes/EtOAc=10/1–6/1) afforded skeleton 5.

191

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With iron; acetic acid

T=60 - 100°C; 2 h; Hide Experimental Procedure

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Rx-ID: 23324284

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NOVARTIS AG; NOVARTIS PHARMA GMBH

Patent: WO2004/78754 A1, 2004 ; Location in patent: Page 48 ; Title/Abstract Full Text Show Details

59.c:59c) 1-(4-Methanesulfonyl-3-trifluoromethyl-phenyl)-propan-2-one

A solution of freshly prepared 1-METHANESULFONYL-4- (2-NITRO-PROPENYL)-2- trifluoromethyl-benzene (59B) (14 g, 45 mmol) in acetic acid (100 ml) is added slowly to a stirred slurry of Iron powder (27.6 g, 495 mmol) in acetic acid (100 ml) at 60 C. The reaction is then stirred at 100 C for 2 hours then allowed to cool and poured onto ice-water (300 ML). After filtration through celite, washing with dichloromethane (500 ml), the organic extract is separated and washed with water (3 x 300 ml) followed by brine (500 ml). The organic extract is dried (MGS04) and concentrated to give a red oil. Chromatography on silica, eluting with ethyl acetatehexane, affords the titled compound as a white solid.

With iron; acetic acid

T=100°C;

Bioorganic and Medicinal Chemistry Letters, 2012 , vol. 22, # 17 p. 5445 - 5450 Title/Abstract Full Text View citing articles Show Details

192

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75%

Stage #1: With sodium tetrahydroborate in methanol

T=20°C; Nef Reaction; 2 h; Stage #2: With dihydrogen peroxide; potassium carbonate in methanol

T=20°C; 18 h; Hide Experimental Procedure

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Rx-ID: 35934291

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Bhat, Chinmay; Tilve, Santosh G.

Tetrahedron, 2013 , vol. 69, # 30 p. 6129 - 6143 Title/Abstract Full Text View citing articles Show Details

4.3.33 Benzyl (2R)-2-(2-oxobutyl)piperidine-1-carboxylate (19a).

193

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Hide Experimental Procedure

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Rx-ID: 25054548

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Beecham Group P.L.C.

Patent: US4622342 A1, 1986 ; Title/Abstract Full Text Show Details

1-(4-n Decyloxyphenyl)propan-2-one

1-(4-n Decyloxyphenyl)propan-2-one The title compound, bp 190°-5°/1 mm, was prepared from 1-(4-n decyloxyphenyl)-2-nitroprop-1-ene by an analogous procedure to that described in Description 5. 1 Hnmr τ(CDCl ): 8.0-9.3 (19H, complex), 7.85 (3H, s), 6.4 (2H, s), 6.05 (2H, t), 2.8-3.4 (4H, dd). 3

194

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With iron; acetic acid

T=100°C;

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Rx-ID: 33838010

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Bioorganic and Medicinal Chemistry Letters, 2012 , vol. 22, # 17 p. 5445 - 5450 Title/Abstract Full Text View citing articles Show Details

195

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89%

With hydrogenchloride; iron(III) chloride; iron in methanol; water

4 h; Heating;

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Rx-ID: 3268288

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Sircar; Duell; Bristol; Weishaar; Evans

Journal of Medicinal Chemistry, 1987 , vol. 30, # 6 p. 1023 - 1029 Title/Abstract Full Text View citing articles Show Details

196

Synthesize Find similar With iron; acetic acid in methanol; water

Heating;

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Rx-ID: 27987789

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Journal of Medicinal Chemistry, 2008 , vol. 51, # 9 p. 2845 - 2852 Title/Abstract Full Text View citing articles Show Details

Synthesize Find similar

197

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A: 6% B: 7% C: 35%

With titanium(III) chloride in tetrahydrofuran; water

T=0°C; 0.5 h; pH 6.5;

Sera, Akira; Fukumoto, Shoji; Tamura, Masako; Takabatake, Kiyoshi; Yamada, Hiroaki; Itoh, Kuniaki

Bulletin of the Chemical Society of Japan, 1991 , vol. 64, # 6 p. 1787 - 1791 Title/Abstract Full Text Show Details

198

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With chromium dichloride in tetrahydrofuran; water

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Rx-ID: 3683321

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Hauser; Sengupta; Corlett

Journal of Organic Chemistry, 1994 , vol. 59, # 8 p. 1967 - 1969 Title/Abstract Full Text View citing articles Show Details