ok .. so heres the references...
1,3-Benzodioxoles from pyrocatechols. Takeuchi, Junji; Enomiya, Takuji; Nakamura, Takato. (Ube Industries, Ltd., Japan). Jpn. Kokai Tokkyo Koho
(1976), 4 pp. CODEN: JKXXAF JP 51100078 19760903 Showa. Patent written in Japanese. Application: JP 75-23907 19750228. CAN 86:140021
AN 1977:140021 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
JP 51100078 A2 19760903 JP 1975-23907 19750228
Priority Application Information
JP 1975-23907 19750228
Abstract
1,3-Benzodioxoles I (R = CHO, allyl) were prepd. by cyclizing pyrocatechols II with methylene halides and aq. caustic alkali in a polar aprotic solvent while
removing H2O as an azeotrope with the halide. Thus, 0.4 mole II (R = CHO) in Me2SO and 0.93 mole 45.7% aq. NaOH were added to 0.7 mole CH2Cl2 in Me2SO at
reflux over 160 min with azeotropic removal of 42.5 ml H2O. The mixt. was refluxed for 1 h with an addnl. 0.05 mole NaOH and 0.16 mole CH2Cl2 to give 89.7% I (R = CHO), vs. 75% without H2O removal. Similarly, safrole was prepd. in 70.6% yield.
Aromatic alkylenedioxy compounds. Fujita, Harushige; Yamashita, Masataro.
(Japan). Jpn. Kokai Tokkyo Koho (1976), 10 pp. CODEN: JKXXAF JP
51019772 19760217 Showa. Patent written in Japanese. Application: JP
74-89985 19740806. CAN 85:46191 AN 1976:446191 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
JP 51019772 A2 19760217 JP 1974-89985 19740806
Priority Application Information
JP 1974-89985 19740806
Abstract
1,2-(Alkylenedioxy)benzene derivs. I (R1 through R4 = H, halo, lower alkanoyl, alkenyloxy, alkyl, alkenyl, lower alkoxy, NO2, CHO; one of them may be either OH
or Q; 2 adjacent groups be form an alkylenedioxy group; n = 1-6) were prepd. by gradual reaction of 1,2-dihydroxybenzenes II (R5 through R8 = H, halo, lower
alkanoyl, alkenyloxy, alkyl, alkenyl, lower alkoxy, NO2, CHO; one of them may be OH; 2 adjacent groups may form an alkylenedioxy group) with R(CH2)nR (R = halo,
HOSO3) in polar aprotic solvents. I are useful as perfumes and insecticides (no data). Thus, 110 g catechol and 100 g KOH were added to 200 g CH2I2 in DMF over 140-60 min at 110-40* under N, 50 g CH2I2 was added, and the mixt. stirred 30 min to give 80% 1,2-(methylenedioxy)benzene. Among 27 addnl. I prepd. were bis(2,3-methylenedioxyphenoxy)methane, 2,3-(methylenedioxy)anisole, 1,2-dimethoxy-4,5-(methylenedioxy)benzene, and 4-methoxy-2,3-(methylenedioxy)benzaldehyde.
Synthesis of the dihydroxyphenyl (X) from vanillin and Eugenol are not described.... luckily i have the (dihydroxyphenol) aldehyde
[joy] (have sourced a few methods for demethylation from scifinder.. but havent tried them as yet... soon.. hopefully) ...
i will attempt to prepare piperonal from dimethoxybenzaldehyde this weekend... but i welcome others to try as well.... i dont have any of the dimethoxyphenylalkene ... but i will sourse some preps for that and attempt some safrole preps from Eugenol
as well.... again.. others feel free to attempt these
..
your thoughts on these rxns and workup will be nice
regards..
