Hydroxy-ethanethiol

A slurry of the Merrifield resin (2.9 mmol) in 20 ml of dry DMF was treated with 2-hydroxy-ethanethiol (15.25 mmol), K2CO3 (14.5 mmol), and pyridine(12.9 mmol), and the suspension was stirred for 4 hours at 95°C. It was then left stirring overnight at 20°C. The resin was filtered and washed extensively with DMF, CH2CI2, water, water/ methanol, 1 1, and methanol. The material was dried under vacuum at 50°C and 3.92 g of product were isolated. 

Materials. The synthesis of the p-CD adsorbate is described in references 12, 13, and 14. 6-ferrocenyl-hexanethiol (Fc) was synthesized according to the literature [15] 8-anilino-l-naphthalenesulfonic acid (1,8-ANS), 2-hydroxy-ethanethiol, and octadecanethiol were purchased from Aldrich and used as received. 

Cyclic Voltammetry [12]. The composition of the mixed monolayer of 6-ferrocenyl-hexanethiol and 2-hydroxy-ethanethiol used in the AFM-measurements was determined by separate cyclic voltammetric experiments. The redox signal of the ferrocene unit was integrated in cyclic voltammograms measured in 0.1 M NaC104 for monolayers of different ratios of the two adsorbates in the adsorption solution (1-100% Fc). 

The complexation behavior of SAMs of P-CD 1 was measured by single molecule force spectroscopy (Figure 4). Gold-coated AFM tips were modified with a mixed SAM of 2-hydroxy-ethanethiol and 6-ferrocenyl-hexanethiol. As shown by cyclic voltammetry experiments the mixed SAMs contained 1 % - 2 % 6-ferrocenyl-hexanethiol. The dilution was carried out in order to reduce the number of possible interactions and to maximize the conformational freedom of the immobilized ferrocene moieties. 

Control experiments were carried out with 2-hydroxy-ethanethiol and octadecanethiol modified tips (no guest) on P-CD SAMs and with mixed 2-hydroxy-ethanethiol and 6-ferrocenyl-hexanethiol modified tips on octadecanethiol and 2-hydroxy-ethanethiol SAMs (no host). The corresponding force distance curves showed normal" (single) pull-offs which indicated the absence of specific interactions (Figure 7). The magnitude of the pull-off forces in the control experiments is characteristic for interactions measured in water [23]. 

Figure 7. Force-distance curves obtained in control experiments on pure fi-CD 1 SAMs on Au(l 11) using octadecanethiol (A) and 2-hydroxy-ethanethiol functionalized tips (B) [no guest], and on octadecanethiol (C) and 2-hydroxy-ethanethiol (D) SAMs on Au(l 11) using the mixed hydroxyl-ferrocene-modifled tips [no host]. (Adapted with permission from reference 11. Copyright 2000 American Chemical Society.)...

Syn 3-(EthyltHloniethyl)-4-hydroxy-6-pt)enyl-2-hexanone (4) and anti (5) To ethanethiol (10 0 mg 0 17 mmol) in THF (2 mL) was added 1 54 M n butyltittnum m hexane (0 11 mL) at 0 C under Ar Stannous triflate (69 0 mg 017 nvnol) was added and alter 20 mm the mocture was cooled to 4S°C Methyl vinyl Ketone 1 (118 mg 1 98 mmol) m THF (1 5 mL) was added followed by 3 phenyiptopanal 3 350 mg 2 61 mmol) m THF (1 S mL) Alter 12 h aq cilnc acid was added and the organic material extracted with OHjClj The resxlue after evaporation was dissolved in MeOH and treated with citric acxt After 30 min stimng, the mixture was quenched with pH 7 phosphate buffer extracted with CH2CI2, the solvent evaporated and the residue chromatographed to afford 336 mg ot 4 (75%), syn anti (90 10)... 

Dipping solution Make 0.1 g o-phthalaldehyde (phthaldialdehyde, OPA) and 0.1 ml 2-mercaptoethanol (2-hydroxy-l-ethanethiol) up to 100 ml with acetone. 

A rather special procedure for the preparation of 21-hydroxy-20-ketopreg-nanes starts with the 17a-ethoxyethynyl-17 -hydroxy steroids described earlier. Free radical addition of ethanethiol to the triple bond, followed by acid-catalyzed hydrolysis and dehydration gives the 20-thioenol ether 21-aldehyde. This can be reduced with lithium aluminum hydride to the C-21 alcohol and then hydrolyzed to the C-20 ketone in the presence of mercuric chloride. The overall yield, without isolation of intermediates, is in the order of 50% ... 

Hydroxy-20-ketones via Ethoxyethynyl Carbinols A solution of 3, 17/ -dihydroxy-21-ethoxy-17a-pregn-5-en-20-yne 3-acetate (5 g) in ethanethiol (10 g) to which di-t-butyl peroxide (0.95 g) has been added is refluxed for 4 hr... 

Reaction of 56 with thiols in dichloromethane gives the analogous alkyl-thiomethyl and cycloalkylthiomethyl derivatives [e.g., treatment with ethanethiol gives A -(2-hydroxyethylthiomethyl)vinblastine (57)] (75). Compound 56 is also a useful intermediate for the preparation of N-1-furanyl derivatives. For example, treatment of 56 with furfuryl alcohol in methylene chloride in the presence of trace acid gives N -[(5-hydroxy-methyOfurfuryl]vinblastine (58). 

Fluorine bonded to higher condensed ring systems can also be replaced. Thus, 5-fluoro-3-mcth-oxy-7,12-dimethylbenz[ ]anthracene reacts with the sodium salt of ethanethiol in dimethyl-formamidc (155°C, 3 h) to yield 5-(eLhylsull anyl)-3-hydroxy-7,12-dimethylbcnz[ ]anthraccnc (58% mp 118-121 °C).y... 

Under a nitrogen blanket, a mixture of 3 g of 4-(2-piperidinoethoxy)benzoic acid hydrochloride, 2 drops of dimethylformamide, 2.5 ml of thionyl chloride and 40 ml of chlorobenzene was heated at 70°-75°C for about one hour. The excess thionyl chloride and 15-20 ml of solvent were then distilled off. The remaining suspension was cooled to ambient temperature, and to it were added 100 ml of dichloromethane, 2.7 g of 6-methoxy-2-(4-methoxyphenyl) benzo[b]thiophene and 10 g of aluminum chloride. The solution was stirred for about one hour, 7.5 ml of ethanethiol was added, and the mixture was stirred for 45 minutes more. Then 40 ml of tetrahydrofuran was added, followed by 15 ml of 20% hydrochloric acid, with an exotherm to reflux. Fifty ml of water and 25 ml of saturated aqueous sodium chloride was added. The mixture was stirred and allowed to cool to ambient temperature. The precipitate was collected by filtration and washed successively with 30 ml of water, 40 ml of 25% aqueous tetrahydrofuran, and 35 ml of water. The solids were then dried at 40°C under vacuum to obtain 5.05 g of product, which was identified by NMR as 6-hydroxy-2-(4-hydroxyphenyl)-3-[4-(2-piperidinoethoxy)benzoyl] benzo[b]thiophene hydrochloride melting point 217°C. 

During a synthesis of quinone imine precursors to the Dynemicins, Myers and co-workers100 encountered problems with the lability of the dimethyl acetal function in 56,1 [Scheme 1.56] whilst removing the robust phenolic methyl group using sodium ethanethiolate in hot DMF, However prior conversion of the free hydroxy function in the substrate to the magnesium salt 56.2 by reaction with ethylmagnesium bromide afforded protection for the dimethylacetal under the strenuous conditions of nucleophilic demethylation. 

SYNS EMERY 5791 1-ETHANOL-2-THIOL 2-HYDROXY-l-ETHANETHIOL 2-HYDROXYETHYL MERCAPTAN 2-ME MERCAPTOETHANOL P-MERCAPTOETHANOL MONOTfflOETHYLENE-GLYCOL 2-THIOETHANOL TfflOGLYCOL (DOT)... 

HYDROXY-1-ETHANETHIOL see MCN250 HYDROXY ETHER see EES350... 

The latter reaction sequence was of importance since addition of the thiol glutathione to arene-oxide intermediates under control of hepatic glutathione-S-epoxide transferase enzyme(s) is a very important metabolic transformation. It would appear probable that most of the structures of the arene oxide-glutathione adducts (premercapturic acids) reported in the literature before 1975 are incorrect with respect to the position of the hydroxy and thioether substituents (they should now be reversed). Addition of thiomethoxide anion to arene oxide 70 may occur via 1,6- and 1,4-addition, although one of these thioether adducts could also be accounted for by the alternative arene-oxide intermediate obtained from an oxygen-walk. Styrene 3,4-oxide (S3) has been observed to react with ethanethiol to yield three adducts which appear to aromatize to three isomeric ethylthiostyrenes without the formation of episulphonium intermediates. ... 

Synonyms 2-ME Mercaptoethanol l-Ethanol-2-thiol 2-Hydroxy-1-ethanethiol 2-Hydroxyethyl mercaptan Monothioethyleneglycol 2-Thioetha-nol Thioglycol... 

HYDROXY-l-ETHANETHIOL (60-24-2) Combustible liquid (flash point 165°F/ 74°C). Violent reaction with strong oxidizers. Incompatible with strong acids, caustics, aliphatic amines, isocyanates. 

DBU (1) was used as a base in the dehydrochlorination/ring closure of chiral chlorohydrins with high retention of optical purity [60]. A -Acyl-p-hydroxy-4-phenyloxazolidinethiones are rapidly converted into the corresponding ethyl thioesters in high yields by treatment with ethanethiol (EtSH) in the presence of a catalytic DBU (1) [61] (Scheme 3.37). Thus, the chiral auxiliary could be removed cleanly and non-destmctively. 

Hydroxy-1-ethanethiol. See 2-Mercaploethanol Hydroxy ether. See Ethoxyelhanol 2-[2-(2-(2-Hydroigrethox] ethoxy) ethoxy] ethanol. See PEG-4 2-[2-[2- -Hydroxyethox ethoxy] ethoxy] ethyl dodecanoate. See PEG-... 

---