9-Thiabicyclo 3.3.1 nonane

Thiabicyclo[3.1.0]hex-3-ene synthesis, 4, 784 9-Thiabicyclo[3.3.1]nonane 9,9-dioxide bond angles, 7, 409 5-Thiabicyclo-2-pentene, 1,2,3,4-tetrakis(trifiuoromethyl)-rearrangement, 7, 153 2H-l,2-Thiaborin dibenzo fused, 1, 658 1-Thia[2.2.2]cyclazines, 4, 479 5-Thia[2.3.3]cyclazines, 4, 481 Thiacyclobutadienes — see lH-1 A -Thietes... 

C. c a-9-Thiabicyclo. . (S nonane Ben2o o thiopheMe oiB-octahydro- A 3-1., three-necked, round-bottomed flask is fitted with a mechanical... 

D. ci - -Thiabicyclo[4 .. Q]nonan S,S-Dioxide [Benzo[c]thiophene 2,2-dioxide, cis-octahydro-]. A solution of the sulfide (43.0 g., 0.303 mole) in 11. of ether is cooled to 0° and treated dropwise while magnetically stirred with 1.01. of 0.65iV ethereal monoperphthalic acid (0.65 mole). The mixture is kept overnight at 0°, after which time the precipitated phthalic acid is separated by filtration and the filtrate concentrated with a rotary evaporator. Bulb-to-bulb distillation of the residual oil at 0.05-0.1 mm. affords the sulfone as a eolorless liquid (48.5-50 g., 92-95%) (Note 11). This product is crystallized from ether-hexane to give a colorless solid, m.p. 39-41° (Note 12). 

Cyclooctane Sulfide (9-Thiabicyclo[3.3.1]nonane) from 1,5-Cyclooctadiene... 

Treatment of 1,5-cyclopentadiene with sulfur monochloride and then with sulfuryl chloride provided high yields of 2,6-dichloro-9-thiabicyclo[3.3.1]nonane 66 containing a six-membered tetrahydrothiopyran ring (2006MI212). The formation of thiopyran 66 is assumed by the authors to be the result of the reversible elimination-addition of SCI2, which is in equilibrium with sulfur monochloride, and of the high thermodynamic stability of 66 relative to the other monomeric and oligomeric sulfur dichloride addition products (Scheme 34). 

Dimethyl sulfate, 56, 62 Dimethyl sulfide, 56, 16 7,9-Dimethyl-cis-8-thiabicyclo[4 3 0] nonane 8,8-dtoxide, 57, 55... 

A mixture of ci -octahydrobenzo[6]thiophene (48) and cis-2-thiabicyclo[3.3.2]nonane (49a) results from the treatment of 3-/3-chlo-... 

Thiiranes can be formed directly and stereospecifically from 1,2-disubstituted alkenes by addition of trimethylsilylsulfenyl bromide, formed at -78 C from reaction of bromine with bis(trimethylsilyl) sulfide (Scheme 7).12 A two-step synthesis of thiiranes can be achieved by addition of succinimide-A/-sulfe-nyl chloride or phthalimide-A -sulfenyl chloride to alkenes followed by lithium aluminum hydride cleavage of the adducts (Scheme 8).13 Thiaheterocycles can also be formed by intramolecular electrophilic addition of sulfenyl chlorides to alkenes, e.g. as seen in Schemes 914 and 10.13 Related examples involving sulfur dichloride are shown in Schemes 1116 and 12.17 In the former case addition of sulfur dichloride to 1,5-cyclooctadiene affords a bicyclic dichloro sulfide via regio- and stereo-specific intramolecular addition of an intermediate sulfenyl chloride. Removal of chlorine by lithium aluminum hydride reduction affords 9-thiabicyclo[3.3.1]nonane, which can be further transformed into bicyclo[3.3.0]oct-1,5-ene.16... 

Successive treatment with either SC12 or S2CI2 and SOCl2 converts 1,5-cyclooctadiene into 2,6-dichloro-9-thiabicyclo-[3.3.1]nonane 466. Both halogen atoms can be replaced by a wide variety of nucleophiles <2001JOC4386>. Following hydrolysis to the 2,6-diol, Swern oxidation affords the 2,6-dione (Scheme 160) < 19980SC692>. 

When di-te -butyl sulfoxide is heated in 1,5-cyclooctadienc at 148 °C for 1.5 hours, 9-thiabicyclo-[4.2.1]nonane anti-9-oxide (6) is obtained as the only bicyclic sulfoxide after chromatography91. 

Other nuclei besides H or have been used to monitor enantiomeric discrimination with chiral lanthanide chelates. This includes the NMR spectra of chiral 2-thiabicyclo[4.3.0]nonane 2,2-dioxides (14) and 8,8-dioxides (15) with Pr(hfc)3 . The Si NMR spectrum of a-C-silylated amines and alcohols (38) in the presence of Eu(tfc)3 was used to monitor the optical purity of these compounds . A refocused-decoupled INEPT (insensitive nuclei enhanced by polarization transfer) pulse sequence was used to circumvent the long spin-lattice relaxation times of the silicon. 

The basicity of the sulfoxide oxygen has been investigated by observing infrared shifts in protic solvents. ° In this way, it was shown that thietane 1-oxide is more basic than cyclobutanone, but less basic than tetramethylene sulfoxide (thiolane 1-oxide) or pentamethylene sulfoxide (thiane l-oxide). ° Toward phenol, the order of basicity is as follows thiolane 1 -oxide > diethyl sulfoxide > thiepan 1-oxide > dimethyl sulfoxide > thiane 1-oxide > 9-thiabicyclo[3.3.1]nonane 9-oxide > 7-thiabicyclo[2.2.1]heptane 7-oxide > thietane 1-oxide.ThepKaof the conjugate acid of thietane 1-oxide is — 1.92, as determined in aqueous sulfuric acid. =... 

Octahydro- (we have used this nomenclature throughout) or perhydrobenzo[c]thiophene (35) exists as the cis and trans isomers and is more commonly named 2-thiahydrindane or 8-thiabicyclo-[4.3.0]nonane. Each stereoisomer may be prepared by treating the corresponding isomer of l,2-di(bromomethyl)cyclohexane with sodium sulfide (details of the products are given in Table IV).45 Cyclization of the cis isomer may be effected partially with thiourea via the formation of cis-hexahydro-o-xylylenebis(isothiouronium bromide) with sodium disulfide it gives a mixture of cis-octahydro-benzo[c]thiophene and cis-2,3-dithiadecalin.46 Optically pure ( —)-(8 R,9I )-lran -octahydrobenzo[c]thiophene has been prepared from (+ )-dicarboxylic acid via reduction of the diacid to the diol, tosylation, and ring closure of the bistosylate with sodium sulfide.47... 

Thus, ran5-2-trimethylsilyl-4,5-epoxythiacyclononane 1,1-dioxide (6) on treatment with 0.3 equivalents of potassium /ert-butoxide as desilylating agent in tetrahydrofuran at — 10°C for 1.5 hours gave a mixture containing (la,7/S,8a)-2-thiabicyclo[6.1.0]nonan-7-ol 2,2-dioxide (7) as the major product (68%), together with cis- and f/ a . -2-thiabicyclo[4.3.0]nonan-5)S-ol 2,2-dioxides 8 (12 and 20%, respectively). ... 

At lower temperature, treatment of this silylated sulfone epoxide 6 with 0.8 equivalents of potassium mrr-butoxide for 4 hours gave a new product, (la,7a,8a)-l-trimethylsilyl-2-thiabicyclo[6.1.0]nonan-7-ol 2,2-dioxide (9), together with unrearranged sulfone epoxide 10 arising from protodesilylation, and the desilylated bicyclic hydroxy sulfone 7 in the ratio 78 16 6. 

Disubstituted tetrahydrothiopyrans, synthesis of 83CRV379. Tetrahydrothiopyran-4-one and syntheses based on 85AKZ166. Thiadecalins and 2-thiabicyclo [4.3.0]nonanes, synthesis and reactivity of ... 

A. (1a,2tt,Sa,6a)-2,6-Dichloro-9-thiabicyclo[3.3.1]nonane (1). (Caution Preparation A should be carried out in a well-ventilated hood). A dry, 2-L, four-necked, round-bottomed flask is equipped with a sealed mechanical stirrer (Note 1), 1-L pressure-equalizing tunnel fitted with a drying tube, low temperature thermometer, and a nitrogen inlet. The flask is charged with 125 mL (1.02 mol) of 1,5-cyclooctadiene (Note 2) and 1 L of reagent dichloromethane, cooled to -50 to -60 C using an external acetone-dry ice bath, and the solution placed under a slow stream of dry nitrogen. To... 

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