1,3-benzodioxole to 2-Alkyl-1-(benzo[d][1,3]dioxol-5-yl)ethan-1-one [Reaxys, Reactions (5); 2

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5 reactions in Reaxys

2016-03-07 14h:34m:27s (EST)

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1. Query

Search as: As drawn, No salts, No mixtures

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O O O

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Rx-ID: 34494801 View in Reaxys 1/5 Yield 86 %

Conditions & References With boron trifluoride in 1,2-DICHLOROETHANE, T= -15 - -5 °C , Large scale Storace, Louis; Anzalone, Luigi; Confalone, Pat N.; Davis, Wayne P.; Fortunak, Joseph M.; Giangiordano, Mark; Haley Jr., James J.; Kamholz, Kenneth; Li, Hui-Yin; Ma, Philip; Nugent, William A.; Parsons Jr., Rodney L.; Sheeran, Patrick J.; Silverman, Charlotte E.; Waltermire, Robert E.; Wood, Christopher C.; Organic Process Research and Development; vol. 6; nb. 1; (2002); p. 54 - 63 View in Reaxys

85 %

3 : 1-(Benzo[d][1,3]dioxol-5-yl)butan-1-one (4)16 A pre-dried two-neck round bottom flask was charged with 1,2-methylenedioxy benzene (2.0 g, 16.37 mmol), 1,2dichloroethane (7 mL) and n-butyric anhydride (3.2 mL, 19.6 mmol).

The resulting mixture was cooled to -10 °C, to that BF3·Et2O (6.78 g, 1.38 mmol) was added by slow addition over 15 min, while maintaining the temperature -5 °C to 0 °C. After the addition, the reaction mixture was stirred at -5 °C for 3 h.

The reaction was then quenched with sodium acetate solution, the organic layer was separated and washed with 5percent NaOH (7 mL) followed by water.

The organic layers were concentrated and the crude product was purified by column chromatography using on silica gel with hexane/ethyl acetate (10percent) as eluent to yielded the desired compound 4 (1.34 g, 85percent).

1H NMR (400 MHz, CDCl ), 7.52 (dd, J=8.1, 1.6 Hz, 1H), 7.40 (d, J=8.1 Hz, 1H), 6.80 (d, J=8.1 Hz, 1H), 5.99 (s, 1H), 3 2.82 (t, J=7.3 Hz, 2H), 1.70 (h, J=7.4 Hz, 2H), 0.95 (t, J=7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) 198.4, 151.5, 148.1, 132.0, 124.1, 107.8, 107.7, 101.7, 40.2, 18.0, 13.8; HRMS-ESI-MS (m/z) [M+H]+: calcd for C11H13O3: 193.0865; found 193.0867.

With boron trifluoride diethyl etherate in 1,2-DICHLOROETHANE, Time= 3.25h, T= -5 °C Murugan, Kaliyappan; Huang, Da-Wei; Chien, Yu-Ting; Liu, Shiuh-Tzung; Tetrahedron; vol. 69; nb. 1; (2013); p.

268 - 273 View in Reaxys With AlCl3, aluminium chloride, carbonic acid dimethyl ester, T= 20 °C , Friedel-Crafts Acylation Koura, Minoru; Matsuda, Takayuki; Okuda, Ayumu; Watanabe, Yuichiro; Yamaguchi, Yuki; Kurobuchi, Sayaka; Matsumoto, Yuuki; Shibuya, Kimiyuki; Bioorganic and Medicinal Chemistry Letters; vol. 25; nb. 13; (2015); p. 2668 - 2674 View in Reaxys O

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Rx-ID: 36245590 View in Reaxys 2/5 Yield

Conditions & References 1.A : A. Synthesis of 5-n-octanoyl-1 ,3-benzodioxole In a 500 ml 3-necked reactor equipped with stirring rod, thermometer and reflux condenser, 24.4 g (0.2 moles) of 1 ,3benzodioxole in 120 grams of dichloromethane and 5.6 g (0.04 moles) of anhydrous zinc chloride were added at room temperature and in nitrogen stream. The reaction mixture was then added at room temperature and in the time frame of 2 hours with 37.8 g (0.20 moles) of n- octanoyl chloride It was maintained under agitation at room temperature, for 12 hours and then there were added 75 ml of an aqueous solution of NaOH 3M. The organic phase was separated and washed with 70 ml of water, dried on anhydrous sodium sulphate, vacuum filtered and evaporated ( 25 °C/ 21 mbar).

34 g of dense, oily crude product were obtained, which was used for the successive reaction without further purification.

With zinc(II) chloride in dichloromethane, Time= 14h, T= 20 °C , Inert atmosphere Patent; ENDURA S.P.A.; GOBBI, Carlotta; BORZATTA, Valerio; CAPPARELLA, Elisa; WO2013/135806; (2013); (A1) English

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View in Reaxys 1.A : Synthesis of 5-[2-(2-butoxyethoxv)-ethoxymethyl]-6-n-octyl-1,3-benzodioxole) A. Synthesis of 5-n-octanoyl-1,3-benzodioxole In a 500 ml 3-necked reactor equipped with stirring rod, thermometer and reflux condenser, 24.4 g (0.2 moles) of 1,3benzodioxole in 120 grams of dichloromethane and 5.6 g (0.04 moles) of anhydrous zinc chloride were added at room temperature and in nitrogen stream.

The reaction mixture was then added at room temperature and in the time frame of 2 hours with 37.8 g (0.20 moles) of n-octanoyl chloride It was maintained under agitation at room temperature. for 12 hours and then there were added 75 ml of an aqueous solution of NaOH 3M. The organic phase was separated and washed with 70 ml of water, dried on anhydrous sodium sulphate, vacuum filtered and evaporated (25° C./ 21 mbar).

34 g of dense, oily crude product were obtained, which was used for the successive reaction without further purification.

With zinc(II) chloride in dichloromethane, Time= 14h, T= 20 °C , Reflux, Inert atmosphere Patent; ENDURA S.P.A.; Gobbi, Carlotta; Borzatta, Valerio; Capparella, Elisa; US2015/38465; (2015); (A1) English View in Reaxys O

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Rx-ID: 1651712 View in Reaxys 3/5 Yield 58 %

Conditions & References With tin(IV) chloride in dichloromethane, Time= 1h, T= 20 °C Daukshas; Gaidyalis; Pyatrauskas; Udrenaite; Gasperavichene; Raguotene; Pharmaceutical Chemistry Journal; vol. 21; nb. 5; (1988); p. 341 - 345 View in Reaxys O

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Rx-ID: 1651725 View in Reaxys 4/5 Yield 64 %

Conditions & References With tin(IV) chloride in dichloromethane, Time= 0.25h, T= 10 - 15 °C Daukshas, V. K.; Gaidyalis, P. G.; Udrenaite, E. B.; Labanauskas, L. K.; Gasperavichene, G. A.; et al.; Pharmaceutical Chemistry Journal; vol. 23; nb. 12; (1989); p. 990 - 995; Khimiko-Farmatsevticheskii Zhurnal; vol. 23; nb. 12; (1989); p. 1466 - 1470 View in Reaxys O

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Rx-ID: 22846037 View in Reaxys 5/5 Yield 34.5 g

Conditions & References With perchloric acid, Time= 3h, T= 0 - 20 °C Patent; Endura S.p.A.; US6342613; (2002); (B1) English View in Reaxys With AlCl3, aluminium chloride, carbonic acid dimethyl ester, T= 20 °C , Friedel-Crafts Acylation

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Koura, Minoru; Matsuda, Takayuki; Okuda, Ayumu; Watanabe, Yuichiro; Yamaguchi, Yuki; Kurobuchi, Sayaka; Matsumoto, Yuuki; Shibuya, Kimiyuki; Bioorganic and Medicinal Chemistry Letters; vol. 25; nb. 13; (2015); p. 2668 - 2674 View in Reaxys

Copyright © 2016 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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