1,3-Benzodioxole derivatives

Schill, G., Doerjer, G., Logemann, E., Fritz, H., Studies on the synthesis of molecules with knot structure fourfold bridged 5,6-diamino-l,3-benzodioxole derivatives. Chem. Ber.-Recl. 1979, 112, 3603-3615. 

In the search for chemicals inhibiting the enzymes O-methyl transferase and methyl farnesoate epoxidase, responsible for the methyl ester formation and for the terminal epoxidation in juvenile hormone biosynthesis. Brooks and co-workers (1984) prepared a number of acetylenic esters and 1,3-benzodioxole derivatives. These groupings are of particular interest in the context of JH biosynthesis inhibition. The acetylenic derivative 79 showed the strongest inhibitory action on both enzymes. 

The 1,3-benzodioxole derivatives are oxidatively metabolized by cytochrome P450 monooxygenases with formation of very stable complexes... 

Characterization of the (TPP)Fe(l,3-benzodioxol-2-carbene) complex (Eq. 8) was also reported, giving indirect evidence for the presence of this carbene as a ligand in the benzodioxole-derived cytochrome P450 complex (Eq. 9) [7,16]. 

A carboxylic acid group may be introduced into the 2-position of dibenzofuran by Friedel-Crafts reaction with 2,2-dichloro-l,3-benzodioxole (catechol dichloromethylene ether) and hydrolysis of the resultant ester. Similarly, reaction with methylphenylcarbamoyl chloride produces the 2-(N-methyl-yV-phenylcarboxamide) or the 2,8-disubstituted derivative under more stringent conditions. Controlled reduction of these amides with lithium aluminum hydride supplies the corresponding aldehydes. ... 

The chlorine atoms in 2,2-dichloro-l,3-benzodioxole and its derivatives are replaced upon treatment with antimony(III) fluoride more readily than those in aryl trichloromethyl ethers, which exchange only in the presence of the catalyst antimOny(V) chloride. 

The principal red couplers are 3-aminophenol [591-27-5], 5-amino-2-methyl-phenol [2835-95-2], and 1-naphthol [90-15-3]. Yellow-green couplers include resorcinol [108-46-3], 4-chlororesorcinol 195-88-5, benzodioxoles, and 2-methyl-resorcinol [608-25-3] and its derivatives. The importance of the yellow-green couplers lies in the broad-band absorption of the dyes produced, which makes natural-looking hair shades possible. Table 5.4 lists a range of colors obtained by reaction of primary intermediates with different couplers. 

An additional example is constituted by 2,2-difluoro-4-methyl-l,3-benzodioxole which is deprotonated by sec-butyllithium exclusively at the 7-position, whereas only derivatives of the benzylmetal species are isolated after treatment with LIDA-KOR.204... 

Table 1 Selected (6R-fran5 )-6-(l,3-benzodioxol-5-yl)-2,3,6,7,12,12a-hexahydro-2-pyrazino[l, 2, l,6]pyrido[3,4-b]indole-l,4-dione derivatives their and corresponding physical properties. H NMR data supplied by author...

SYNS ACETYLMETHYLCARBAMIC ACID 2,2-DIMETHYL-L3-BENZODIOXOL-4-YL ESTER CARBAIvnC ACID, ACETYLMETHYL-, 2,2-DIMETHYL-1,3-BENZODIOXOL-4-YL ESTER CARBAMIC ACID, ACETYLMETHYL-, 2,3-(ISOPROPYLIDENE-DIOXY)PHENYL ESTER NC-6897, ACETYL DERIVATIVE... 

The reaction of 4,7-di- -butyl-l,3-benzodioxole with trityl cation results in hydride abstraction from the 2-position to give the dioxolium cation which can be conveniently trapped by alcohols to give the 2-alkoxy derivatives <84IZV1632>. 

The dioxolium salt derived from 2,2-dichloro-l,3-benzodioxole and BCI3 reacts with isobutylene by nucleophilic attack at C-2 to afford (59) after a second attack on the cation (58) <88CB339>. The... 

Access to 1,3-dioxole (7), l,3-dioxol-2-one (8), 1,3-benzodioxole (10), l,3-benzodioxol-2-one (11) and their substituted derivatives was discussed in CHEC-I. Among the new methods to the derived imines and thiones, those based on the tin compounds (270) and described in Section 3.10.8.2 are possibly the best. The diazo compound-based preparations of (273) and (275) (Section 3.10.8.2) represent useful approaches to 1,3-oxathioles, and the corresponding imines (329) and thiones (324) are probably also best prepared from the diazo compounds (312) as described in Section 3.10.8.3. 

An interesting type of insect chemosterilants has been reported by Jurd et al. (1979). They found that benzyl derivatives of 2,4-di-/-butylphenol and of 1,3-benzodioxoles sterilise houseflies when fed at concentrations as low as 0.025% in the diet. The most active members of this group are 2,4-bis(l,l-dimethylethyl)-... 

A short, convenient, stereoselective synthesis of pepper-derived alkaloids has been carried out by condensing piperonal with the ylide from methyl (E)-4-(diethylphosphono)-2-butenoate to give methyl (E,E)-5-(1,3-benzodioxol-5-yl)-2,4-pentadienoate, which on methoxide-catalysed aminolysis (piperidine, pyrrolidine, etc.) gave the required alkaloid. 

Shulgin. 1986. Derivatives of 1-(1,3-benzodioxol-5-yl)-2-butanamine representatives of a novel therapeutic class. J. Med. Chem. 29 2009. 143. XP... 

Methylmagnesium iodide prepared from methyl iodide and magnesium in ether under Ng, the ether replaced by benzene or xylene, 1,3-benzoxathiole added, and refluxed 4 hrs. 2-(ethylthio)phenol. Y 75%. - 1,3-Benzodioxoles behave similarly, except for certain 2,2-disubst. derivs. which are almost completely cleaved to catechols. F. e., also with 1,3-benzodioxoles, s. S. Cabiddu, A. Maccioni, and M. Secci, G. 99, 771 (1969). 

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