Methylenedioxyphenyls

Example 24 Add. 1 mole of 3-(3,4-methylenedioxyphenyl) propylene,. 25 mole of methyl nitrite,. 008 mole palladium bromide as a catalyst,. 5L of methanol and 36g of water to a flask. Stir magnetically for 2 hoursat 25C. Yield of 3,4-methylenedioxyphenylacetone (also known as 3,4-... 

The alcohol intermediate happens to be the exact kind of intermediate that was produced by the Grignard reagent reaction with propanal to produce isosafrole back-a-ways in the big chapter. So what the chemist does is apply the 1g of KHSO4 to that crude alcohol intermediate and process it just as was done before to give isosafrole, or propenylbenzene or 3,4-methylenedioxyphenyl -1-butene or phenylbutene (yield=91% ). This is a great little procedure. 

Cinnamyl—sesamol ethers, eg (35), are useful as insect chemosterilants (111). 3,4-Methylenedioxyphenyl-3-halo-2-propynyl ethers (36, X = halogen) are synergists for carbamate insecticides (112). HaloaLkyl or haloalkenyl ethers, eg (37), show acaricidal and insect juvenile hormone activity (113). The first total synthesis of gibbereUic acid was from 2-methoxy-6-aLkoxyethyl-l,4-benzoquinone, a derivative of hydroxyhydroquinone (114). 

Benzo[b]furan, 2-(3,4-methylenedioxyphenyl)-5-( 1,3-dihydroxypropyl)-7-methoxy— see Machicendiol... 

Mammals and some Malathion Carboxylesterase methylenedioxyphenyls Some OPs other than <200... 

Glennon, R.A. Yousif, M. and Patrick, G. Stimulus properties of /-(3,4-methylenedioxyphenyl)-2-aminopropane (MDA) analogs. Pharmacol Biochem Behav 29 443-449, 1988. 

In the search for safe insecticides the authors have prepared hundreds of new products and subjected them to preliminary screening tests against insects. That part of their work dealing with methylenedioxyphenyl derivatives was prompted by the original fundamental studies of 0. F. Hedenburg, with whom they have collaborated in this field. Two materials of this type—piperonyl butoxide (I) and piperonyl cyclonene (II)—have recently been introduced commercially. These products have definite insecticidal properties in themselves, but show their maximum efficiency toward insects and other arthropods when used in combination with pyrethrins. Furthermore, they are at least as nontoxic... 

A striking illustration of the effect of chemical structure on insecticidal properties is provided by the data given in this paper on compounds related to piperonyl butoxide. According to the above theory, the methylenedioxyphenyl nucleus present in this substance is the toxophore. The materials selected for comparison show the reduction in toxicity produced, first, by modifying the toxophore, and, second, by substituting different groups for the auxotox radical. 

The stereoselective intramolecular Henry reactions have been reported by Seebach. The Michael addition of doubly deprotonated acetyl acetaldehyde to l-methylenedioxyphenyl-2-nitroethene followed by subsequent intramolecular nitro-aldol cyclization leads to the diastereomerically pure cyclohexanone derivative, where the nitro and OH groups are cis as shown in Eq. 3.73.114 This reaction is applied to the synthesis of l-desoxy-2-lycorinone as shown in Eq. 3.74.115... 

Figure 4.17 Substrate adsorption synthesis of ((S)-3,4-methylenedioxyphenyl)-2-propanol from 3,4-methylenedioxyphenylacetone applying a batch process followed by a filtration step and resin extraction...

Erdelyi, B., Szabo, A., Birincsik, L. and Hoschke A. (2004) Process development of methylenedioxyphenyl-acetone chiral bioreduction. Journal of Molecular Catalysis B, Enzymatic, 29 (1-6), 195-199. 

Franklin MR. The enzymic formation of methylenedioxyphenyl derivative exhibiting an isocyanide-like spectrum with reduced cytochrome P-450 in hepatic microsomes. Xenobiot-ica 1971 1(6) 581—591. 

A-Ethyl-3,4-methylenedioxyaniline was reacted with EMME in boiling dioxane for 6 hr, in the presence of two drops of a solution of 40% Triton B in methanol, to give 7V-ethyl-/V-(3,4-methylenedioxyphenyl)amino-methylenemalonate in 87% yield [71JAP34707 72JCS(P1)173]. No reaction occurred in the absence of the Triton B catalyst [72JCS(P1) 173] (Scheme 21). 

V-(3,4-Methylenedioxyphenyl)aminomethylenemaIonate (258) was prepared in 81% yield by heating a 1 1 1 mixture of 3,4-methylenedioxyani-line, ethyl orthoformate, and diethyl malonate in the presence of ZnCU at 120-140°C for 4 hr [73JAP(K)15879]. 

When a mixture of 3,4-methylenedioxyaniline, ethyl formimidate, and diethyl malonate was reacted at 110-I20°C for 6 hr, 30% of diethyl malonate and 19% of 3,4-methylenedioxyaniline were recovered. In addition, 18% of /V-(3,4-methylenedioxphenyl)aminomethylenemalonate (258), 11% of formamidine (259), and 7% of /V-(3,4-methylenedioxyphenyl)amino-methylenemalonamate (260) were isolated from the reaction mixture by means of column chromatography (74MI2). 

Labeled /V-(3,4-methylenedioxyphenyl)aminomethylenemalonate (258) was obtained in 54% yield after column chromatography when a 1.2 1 1.2 mixture of 3,4-methylenedioxyaniline, diethyl l4C-malonate, and ethyl orthoformate was reacted at 122-125°C for 7.5 hr in the presence of anhydrous ZnCl2 (74MI2). 

A similar reaction was carried out starting from 3,4-methylenedioxyani-line to afford A -(3,4-methylenedioxyphenyl)aminomethylenemalonate (258) in 83% yield (83MIP2). 

The cyclization of diethyl N-(2,3-methylenedioxyphenyl)aminomethy-lenemalonate in boiling diphenyl ether or Dowtherm A afforded 1,3-dioxo-... 

The heating of N-ethyl-A-(3,4-methylenedioxyphenyl)aminomethy-lenemalonate (286) in boiling phosphoryl chloride for 3 hr gave oxolinic acid in 35% yield after the work-up process (87KFZ1249). 

V-(3-trifluoromethylphenyl)aminomethylenemalonate (749, R = 3-CF3) proved unsuccessful in boiling phosphoryl chloride. The thermal cycliza-tion of ZV-ethyl-N-arylaminomethylenemalonates (749) and their ring closure in acetic acid, in acetic anhydride with zinc chloride, or in a melt of aluminium chloride were likewise unsuccessful (71JHC357). The corresponding quinoline was not obtained in a one-pot version when N-ethylani-line and EMME were reacted in polyphosphoric acid. Table V shows the yields of quinoline-3-carboxylic acid derivatives obtained from /V-ethyl-N-phenyl- and iV-ethyl-7V-(3,4-methylenedioxyphenyl)aminomethylene-malonates (749, R = H and 3,4-0CH20) under various acidic cyclization conditions. 

Cyclization of Diethyl A -Ethyl-JV-phenyl- and iV-ETHYL-A-(3,4-METHYLENEDIOXYPHENYL)AMlNOMETHYLENEMALONATES (749) UNDER Acidic Condition (71JHC357)... 

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