Sodium thioethoxide

Sulfenylation of active methylene compounds. Sulfenylation of active methylene compounds by the sulfenyl transfer reagents 1 ordinarily gives a mixture of mono-and bisulfenylated products in which the latter predominate.1 However, the bisulfenylated products are reduced cleanly by sodium thioethoxide to monosulf-enylated products.2... 

Fig. 3. Visible spectra of 1,3,5-trinitrobenzene (4 x 10-5m) in methanol containing the following molarities of sodium thioethoxide (a) 1,2-5 x 10-4 2,5 x 10-4 3, 2-5 x 10-3 (b) 4, 0-01 5, 0-035 6, 0-1 7, 0-5. These spectra show the conversion of trinitrobenzene to a 1 1 adduct at low base concentration and 1 2 adduct at higher base concentrations.

Fig. 4. NMR spectra (60 MHz) of picramide in methanol-dimethyl sulphoxide containing sodium thioethoxide. Ratio [EtS ]/[Picramide] is (a) 0-75, (b) 1-0. The ring- and amino-protons of the parent absorb at -9-07 p.p.m. and -9-0 p.p.m. respectively, the other bands are due to the adduct, 29. (Crampton, 1968a.)...

The conversion of (—)-apomorphine into (+)-apomorphine has been achieved.56 The O-dealkylation of 10,11-dimethoxyaporphine, using sodium thioethoxide in dimethylformamide, has been reported.57 The reactions of the enamine dehydro-nuciferine with dimethyl acetylenedicarboxylate, methyl propiolate, methyl acrylate, and diethyl azodicarboxylate have been investigated, and have resulted in the preparation of a novel series of 7-substituted aporphines.58... 

Sodium pyridylselenate, 368 Sodium selenophenolate, 368-369 Sodium succinimide, 78 Sodium sulfide, 377 Sodium thioethoxide, 368 Sodium triethylborohydride-Iron(H) chloride, 369... 

DABCO). 1,5-Diazabicy do [5,4,0 ] undec-ene-5 (DBU). Diethylamine. Ethylene-diamine. Lithio propylidene-f-buty limine. Lithium bis(trimethylsilyl)amide. Lithium f-butoxide. Lithium diethylamide. Lithium diisopropylamide. Lithium N-isopro-pylcyclohexylamide. Lithium orthophosphate. Lithium 2,2,6,6-tetramethylpiper-ide. Lithium triethylcarboxide. 1,2,2,6,6-Pentamethylpiperidine. Piperazine. Potassium f-butoxide. Potassium hexamethyldi-silaznae. Potassium hydride. Potassium hydroxide. Pyridine. 4-Pyrrolidopyridine. Quinuclidine. Sodium ethoxide. Sodium methoxide. Sodium thioethoxide. Tetra-methylguanidine. Thallous ethoxide. Tri-ethylamine. 

CHLORO CYCLIC ETHERS Sodium. ETHERS Lithium iodide. Sodium thioethoxide. 

Sodium N-methylanilide, 459 Sodium methylsulfinylmethylide, 195-196 Sodium naphthalenide, 349-350 Sodium nitrite, 459-460 Sodium nitrosodisulfonate, 411 Sodium orthophosphate dodecahydrate, 309 Sodium perborate, 59 Sodium phenanthrenide, 375 Sodium phenoxide, 352 Sodium phenoxides, 86 Sodium sulfide, 77,460-461 Sodium sulfite, 91 Sodium tetraborate, 461 Sodium tetracarbonylferrate(-Il), 461-465 Sodium tetraphenylborate, 81 Sodium thiocyanate, 7 Sodium thioethoxide, 465 Sodium thiophenoxide, 314,460 Sodium thiosulfate, 466 Sommelet reaction, 243 Spiroalkylation, 213-214 Spirobutanones, 211-212 Spiro[l,3-dithiol-2,9 -fluorene], 446 Spiro-epoxy-2,4-cyclohexadienones, 373-374... 

Demethylation of aryl methyl ethers. Koutek and Setinek1 reported that aryl methyl ethers can be demethylated by sodium thioethoxide (C2H5SNa) they used ethanol as solvent and temperatures of 190° (autoclave). However, if DMF is used as solvent, demethylation is complete at reflux temperatures in about an hour.2 Yields are high (94-88%). Ethers of dihydric phenols give selective mono-demethylation. 

This latter type of transformation was first carried out by Davoll, Lythgoe, and Trippett, who prepared 7-(2,3-anhydro-a-D-lyxofuran-osyl)theophylline from 7-( -D-arabinofuranosyl)theophylline, and 7-(2,3-anhydro-j8-D-ribofuranosyl)theophylline from 7-((3-D-xylofuranosyl)theo-phylline, by the same reaction-sequence. These 2,3-anhydronucleosides, on reaction with sodium thioethoxide, give the 3-/S-ethyl-3-thio compounds, so that desulfurization of them gives 3-deoxy-a-D-arabinofuranosyltheo-phylline and 3-deoxy-/3-D-ribofuranosyltheophylline. ... 

Selective O-demethylation of (+ )-0-methyldomesticine (75) with 36% HBr leads to a 37.7% yield of racemic domesticine (76), but O-demethylation with sodium thioethoxide in DMF affords a 71.4% yield of (-l-)-domesticine. ... 

For the direct synthesis of racemic 13-desoxydelphonine (86), the starting material was the pentacyclic intermediate (87) (c/. this Report, 1977, Vol. 7, p. 257). This compound was treated with sodium thioethoxide in DMF to yield (88). Alkylation of (88) with methyl bromoacetate gave (89). Acid hydrolysis... 

The reaction of sodium thioethoxide or sodium thiophenoxide with TNB in protic solvents or in DMSO results in the formation of 1 1 and 2 1 adducts by addition at 1 or 2 ring positions, respectively [84, 159]. With ethylthiopicrate thioethoxide, ions initially yield a mixtnre of the isomeric adducts (60) and (61), and this is followed by substitution of the para-nitro gronp to give 1,4-bisethylthio-2,6-dinitrobenzene [160]. 

Preparation by demethylation of 3,3, 5,5 -tetra-tert-butyl-4,4 -dimethoxy-benzophenone (SM) by means of sodium thioethoxide, under nitrogen, in refluxing N,N-dimethylformamide for 15 h (95%). SM was obtained by a two-step synthesis at first, total methylation of 3,3, 5,5 -tetra-tert-butyl-4,4 -dihydroxydiphenyl-methane with methyl iodide in the presence of sodium hydride, under nitrogen, in refluxing tetrahydrofuran for 2 h. Then, by adding a solution of chromium trioxide in dilute sulfuric acid to an acetonic solution of the dimethyl ether previously formed (82%) and stirring at r.t. for 70 h, one obtains the expected ketone SM (86%) [334]. 

---