Methylene blue synthesis

Faujasite-hosted methylene blue synthesis, optical spectra and spectral hole burning... 

Synthesis. The method of synthesis for Methylene Blue described in reference 14 is stiU the stepwise method of choice for thiazine dyes. /V,/V-Dimethy1-y-pheny1ene diamine [99-98-9], CgH22N2, reacts with sodium thiosulfate [7772-98-7] to form the thiosulfonic acid which condenses with /V, /V-dimetby1 ani1 ine [121 -69-7], CgH N, in the presence of sodium dichromate [10588-01-9] to the indamine, then with copper sulfate [18939-61 -2] and sodium dichromate to Methylene Blue (26). 

The standard procedure for the synthesis of leuco dyes related to benzoyl leuco Methylene Blue is straightforward. The one-pot synthesis is carried out in a two-phase water-toluene system. Methylene Blue is first dissolved in the aqueous phase and reduced with sodium dithionite under nitrogen and with stirring. The yellowish leuco is extracted into the organic phase where it is allowed to react with an acid chloride, the aqueous phase being made alkaline. 

Leuco Methylene Blue, Basic Blue 3, or phenazine dyes are capped with a dye bearing acid chloride or chlorocarbonyl functionality. Normal procedures employed for the synthesis of benzoyl leuco Methylene Blue can be utilized except that a dye chloroformate (69) replaces the benzoyl chloride. 

Scheme 77. Synthesis of protopine alkaloids by photooxygenation of indenobenzazepines. Reagents a, hv, 02, Methylene Blue b, LAH c, Mn02.

Scheme 10. Total synthesis of artemisinin by Schmid and Hofheinz. Conditions (i) ClCH20Me, PhN(CH3)2, DCM, rt. (ii) B2H6/THF, H2O2 (iii) PhCHzBr, KH, THF/DMF (iv) HCl, MeOH (v) PCC, DCM, rt. (vi) LDA, (E)-(3-iodo-l-methyl-l-propenyl)-trimethylsilane (vii) lithium methoxy(trimethylsily)methyhde (viii) Li/NH3 (ix) PCC DCM (x) m-CPBA, DCM (xi) -Bu4NF, THF, rt. (xii) O2 (methylene blue, DCM, rt.) (xiii) HCOOH, DCM.

Paul Ehrlich demonstrated the effective use of methylene blue in the treatment of malaria. He also synthesized arsenical compounds (neoarsphenamine) effective in the treatment of syphilis. The synthesis of newer and powerful antibacterial substances gave the recognition to Paul Ehrlich as the father of modern chemotherapy and awarded the Nobel prize of medicine in 1909. 

C-155 and S-155 materials showed a sponge like structure as the microphotograph of figure 4-B, but when S-155 was submitted to methylene blue adsorption test it did not show adsorption properties C-155 material instead showed a high adsorption activity. The last observation demonstrates that carbon structure is the responsible of the adsorptive behaviour and that the silica structure in this case acts only as an inert skeleton, but at the same time, silica was the responsible of the expanded carbon network developed during the synthesis of the composite. 

In 1929, Fiske and Subbarow,d/f h curious about the occurrence of purine compounds in muscle extracts, discovered and characterized ATP. It was soon shown (largely through the work of Lundsgaard and Lohman)f that hydrolysis of ATP provided energy for muscular contraction. At about the same time, it was learned that synthesis of ATP accompanied glycolysis. That ATP could also be formed as a result of electron transport became clear following an observation of Engelhardth i in 1930, that methylene blue stimulated ATP synthesis by tissues. 

Synthesis of derivatives of methylene blue (MTB) labelled with 211 At,1261 (or1271, stable) and1311... 

The method of sulfide determination is based on what is commonly known as Lauth s reaction, and is adapted from the original method of Fisher (42). It involves a specific use of S in the synthesis of methylene blue from N,N-dimethylphenylenediamine (Fogo and Popowsky (43)). Cysteine, oxidized and reduced glutathione, insulin, and bovine serum albumin do not react in this test, thus indicating its specificity for sulfide (Lovenberg, Buchanan, and Rabinowitz (63)). 

The special effects of a mesoionic system as a substituent have been noted in the reactions with nucleophiles of 3-7V (4-chloro-3-nitrophenyl)sydnone. A synthesis, using two amino-debromination reactions, has been used to prepare phenothiazines analogous to methylene blue (23). An imusual susceptibihty to the nature of the counteranion has been observed in the kinetics of the reaction of iV-(2,4-dinitrophenyl)-4-dimethylaminopyridinium salts (24) with piperidine in acetonitrile, and may indicate participation of the anion in stabilising the intermediate. An ANRORC mechanism is imphcated in the reaction of A-(2,4-dinitrophenyl)-4-(4-pyridyl)pyridinium cations with arylamines. Ring-opening and ring-closure reactions... 

In the same year Caro [27] produced methylene blue, basing his process on the sulphuretted hydrogen reaction observed by Lauth in 1876 [28]. Almost simultaneously malachite green was discovered by E. and O. Fischer. [29] and by Doebner [30] and O. N. Witt and Roussin introduced the synthesis of azo-dyes on a manufacturing scale, which proved afterwards to be of such great importance. 

The iV-subsii lined anilines, available since the mid-1860s, became important intermediates in the manufacture of both the new triarylmethane and the azo colorants. /v,/v-Dimethylanilinc (32) was used by Caro to synthesize the thiazine dye methylene blue (33), the first colorant for which a patent was granted under the new German patent law (Scheme 11). In 1877, Otto Fischer achieved the synthesis from benzaldehyde and 32... 

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