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All 3 posts Subject: MMDA-2: 6-bromopiperonal from piperonal Please login to post Down

3base
(Hive Bee)
06-11-02 11:03
No 319795
      MMDA-2: 6-bromopiperonal from piperonal
(Rated as: good read)

6-bromopiperonal

a solution of 10mL Br2 and 1g I2 in 20mL CS2 was added dropwise
over 30min to a stirred solution of 20g piperonal in 50mL CS2
at room temperature. after the mixture had been stirred for 24h,
it was evaporated under reduced pressure to give a residual red-
brown solid which on 2 recrystallizations from EtOH yielded 12g
6-bromopiperonal as needles, mp 127-129°C, lit(14) mp 129-130°C.

(14) ber, 1891 24: 2592; a oelker

j org chem, 1965 30(6): 1759-1763
"synthesis of dehydrootobain"
derek brown, robert stevenson

... 6-bromopiperonal ... prepared according to orr et al (8) ...

(8) j chem soc, 1917: 946; a m b orr, r robinson, m w williams

j org chem, 1958 23(7): 1012-1014
"preparation of the chrysanthemumates of 6-bromo- and
6-chloropiperonyl alcohols"; W F BARTHEL, B H ALEXANDER

3base
(Hive Bee)
06-11-02 11:45
No 319802
User Picture       ref: 6-bromopiperonal

... 6-bromopiperonal ... prepared according to orr et al (8) ...

(8) j chem soc, 1917: 946; a m b orr, r robinson, m w williams

j org chem, 1958 23(7): 1012-1014
"preparation of the chrysanthemumates of 6-bromo- and
6-chloropiperonyl alcohols"; W F BARTHEL, B H ALEXANDER

Rhodium
(Chief Bee)
10-20-03 12:21
No 465752
User Picture       6-Bromo- to 6-Methoxy-piperonylic acid
(Rated as: good read)

Unfortunately it might not be possible to methoxylate 6-bromopiperonal to 6-methoxypiperonal, the MMDA-2 precursor. The aldehyde function might just be too sensitive towards oxidation to the acid. There are no literature references for the transformation anyway, only for the corresponding acid, which follows here:

6-Bromo-Piperonylic acid to 6-Methoxy-Piperonylic acid
J. Org. Chem. 61, 1004-1013 (1996)

Bromination [37] and sodium chlorite oxidation [38] of piperonal furnished [6-Bromopiperonylic acid], which was transformed to [6-Methoxypiperonylic acid] by copper-catalyzed methoxide ion displacement of bromine [39].

2-Methoxy-4,5-(methylenedioxy)benzoic acid [6-Methoxypiperonylic acid]

To a stirred solution of 5.08 g (221 mmol) of Na metal dissolved in 400 mL of anhydrous methanol was added 6-bromopiperonylic acid [47] (18.0 g, 73.7 mmol). Once the acid had dissolved, Cu powder (2.32 g, 36.5 mmol) was added and the mixture was heated at reflux for 18 h. The mixture was cooled, filtered through Celite, and concentrated to a white paste which was dissolved in 400 mL of water and acidified to pH 3 with concentrated HCl. The free acid was extracted with ethyl acetate, dried (Na₂SO₄), and concentrated to a white powder. Recrystallization (EtOH/water) provided 11.0 g (76%) of the pure 2-methoxy-4,5-methylenedioxybenzoic acid as a colorless solid: mp 152 °C (lit. [48] mp 148-149 °C);

References
(37) Becker, D.; Hughes, L. R.; Raphael, R. A. J. Chem. Soc., Perkin Trans. 1, 1674 (1977)
(38) Pinnick, H. W.; Childers, W. E.; Bal, B. S. Tetrahedron 37, 2091 (1981)
(39) Mayer, W.; Fikentschen, R. Chem. Ber. 91, 1536 (1958)
(47) Dallacker, F. Ann. 14, 633 (1960)
(48) Arnold, R. T.; Bortnick, N. J. Am. Chem. Soc. 67, 1798 (1945)

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	All 3 posts		Subject: MMDA-2: 6-bromopiperonal from piperonal		Please login to post		Down


		3base (Hive Bee) 06-11-02 11:03 No 319795				MMDA-2: 6-bromopiperonal from piperonal (Rated as: good read)
						6-bromopiperonal a solution of 10mL Br2 and 1g I2 in 20mL CS2 was added dropwise over 30min to a stirred solution of 20g piperonal in 50mL CS2 at room temperature. after the mixture had been stirred for 24h, it was evaporated under reduced pressure to give a residual red- brown solid which on 2 recrystallizations from EtOH yielded 12g 6-bromopiperonal as needles, mp 127-129°C, lit(14) mp 129-130°C. (14) ber, 1891 24: 2592; a oelker j org chem, 1965 30(6): 1759-1763 "synthesis of dehydrootobain" derek brown, robert stevenson ... 6-bromopiperonal ... prepared according to orr et al (8) ... (8) j chem soc, 1917: 946; a m b orr, r robinson, m w williams j org chem, 1958 23(7): 1012-1014 "preparation of the chrysanthemumates of 6-bromo- and 6-chloropiperonyl alcohols"; W F BARTHEL, B H ALEXANDER



		3base (Hive Bee) 06-11-02 11:45 No 319802				ref: 6-bromopiperonal
						... 6-bromopiperonal ... prepared according to orr et al (8) ... (8) j chem soc, 1917: 946; a m b orr, r robinson, m w williams j org chem, 1958 23(7): 1012-1014 "preparation of the chrysanthemumates of 6-bromo- and 6-chloropiperonyl alcohols"; W F BARTHEL, B H ALEXANDER



		Rhodium (Chief Bee) 10-20-03 12:21 No 465752				6-Bromo- to 6-Methoxy-piperonylic acid (Rated as: good read)
						Unfortunately it might not be possible to methoxylate 6-bromopiperonal to 6-methoxypiperonal, the MMDA-2 precursor. The aldehyde function might just be too sensitive towards oxidation to the acid. There are no literature references for the transformation anyway, only for the corresponding acid, which follows here: 6-Bromo-Piperonylic acid to 6-Methoxy-Piperonylic acid J. Org. Chem. 61, 1004-1013 (1996) Bromination [37] and sodium chlorite oxidation [38] of piperonal furnished [6-Bromopiperonylic acid], which was transformed to [6-Methoxypiperonylic acid] by copper-catalyzed methoxide ion displacement of bromine [39]. 2-Methoxy-4,5-(methylenedioxy)benzoic acid [6-Methoxypiperonylic acid] To a stirred solution of 5.08 g (221 mmol) of Na metal dissolved in 400 mL of anhydrous methanol was added 6-bromopiperonylic acid [47] (18.0 g, 73.7 mmol). Once the acid had dissolved, Cu powder (2.32 g, 36.5 mmol) was added and the mixture was heated at reflux for 18 h. The mixture was cooled, filtered through Celite, and concentrated to a white paste which was dissolved in 400 mL of water and acidified to pH 3 with concentrated HCl. The free acid was extracted with ethyl acetate, dried (Na₂SO₄), and concentrated to a white powder. Recrystallization (EtOH/water) provided 11.0 g (76%) of the pure 2-methoxy-4,5-methylenedioxybenzoic acid as a colorless solid: mp 152 °C (lit. [48] mp 148-149 °C); References (37) Becker, D.; Hughes, L. R.; Raphael, R. A. J. Chem. Soc., Perkin Trans. 1, 1674 (1977) (38) Pinnick, H. W.; Childers, W. E.; Bal, B. S. Tetrahedron 37, 2091 (1981) (39) Mayer, W.; Fikentschen, R. Chem. Ber. 91, 1536 (1958) (47) Dallacker, F. Ann. 14, 633 (1960) (48) Arnold, R. T.; Bortnick, N. J. Am. Chem. Soc. 67, 1798 (1945)

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