Reaction of adamantanone, diamantanone, and their derivatives with thionyl chloride

1987 ◽  
Vol 52 (8) ◽  
pp. 2028-2034 ◽  
Author(s):  
Josef Janků ◽  
Jiří Burkhard ◽  
Luděk Vodička
Keyword(s):  
Hydrogen Chloride ◽  
Carbonyl Group ◽  
Chlorine Atom ◽  
Thionyl Chloride ◽  
Reaction Rate ◽  
Axial Position ◽  
Chlorine Atoms

In reaction of adamantanone, diamantanone, and their chloro or oxo derivatives with thionyl chloride the oxo group is replaced with two chlorine atoms under formation of geminal dichloro derivatives. The presence of a chlorine atom or an oxo group in both ketones reduces the reaction rate. The reaction rate decreases with decreasing distance between the substituent and the carbonyl group. Ketones with chlorine atom in α- or β-axial position do not react with thionyl chloride. The reaction is accelerated by hydrogen chloride whereas in the presence of pyridine no reaction was observed.

Preparation of Chloro and Sulfanyl Derivatives of 1-(2-Deoxy-4-C-hydroxymethyl-α-L-threo-Pentofuranosyl)uracil

1997 ◽  
Vol 62 (7) ◽  
pp. 1114-1127 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Jan Balzarini ◽  
Antonín Holý
Keyword(s):  
Nucleophilic Substitution ◽  
Hydrogen Chloride ◽  
Thionyl Chloride ◽  
Sodium Methoxide ◽  
Thioacetic Acid ◽  
Uracil Derivatives ◽  
Derivatives Of ◽  
Hiv 1

3'-Chloro and 3'-acetylsulfanyl derivatives of 1-(2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil were prepared by reaction of 2,3'-anhydro-1-{5'-O-benzoyl-4'-C-[(benzoyloxy)methyl]-2'-deoxy-α-L-erythro-pentofuranosyl}uracil (3) with hydrogen chloride and thioacetic acid, respectively. The reaction with hydrogen chloride gave a mixture of N-1 and N-3 substituted uracil derivatives 12 and 14. Reaction of 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-α-L-threo-pentofuranosyl}uracil (7) with thionyl chloride and subsequent debenzoylation afforded 1-(4-C-chloromethyl-2-deoxy-β-D-erythro-pentofuranosyl)uracil (19). Nucleophilic substitution with lithium thioacetate, followed by deacylation, converted 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (9) into 1-(2-deoxy-4-C-sulfanylmethyl-β-D-erythro-pentofuranosyl)uracil (21). The obtained thiols were oxidized with iodine or air to give 1,1'-[disulfandiylbis(2,3-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-3,1-diyl]di(pyrimidine-2,4-(1H,3H)-dione) (17) and 1,1'-[disulfandiylbis(2,5-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-5,1-diyl]di(pyrimidine-2,4(1H,3H)-dione) (22). Reaction of 1-{3-acetylsulfanyl-5-O-methanesulfonyl-4-C-[(benzoyloxy)methyl]-2,3-dideoxy-α-L-threo-pentofuranosyl)}uracil (24) with methanolic sodium methoxide afforded 1-(3,5-anhydro-2,3-dideoxy-4-C-hydroxymethyl-3-sulfanyl-α-L-threo-pentofuranosyl)uracil (25). The same reagent was used in the preparation of 1-(3,5-anhydro-2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil (26) from 1-{4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (8). From the series of 4'-substituted 2'-deoxyuridine derivatives, synthesized in this study, solely the 4'-chloromethyl derivative 19 and the oxetane derivative 26 exhibited an appreciable activity against HIV-1 and HIV-2.

Three new staphylonuclear chloromolybdates : K6Mo3Cl12, (NH4)7Mo3Cl13,H2O, and Cs6Mo4Cl16

1965 ◽  
Vol 18 (3) ◽  
pp. 271 ◽  
Author(s):  
IR Anderson ◽  
JC Sheldon
Keyword(s):  
Solid State ◽  
Hydrochloric Acid ◽  
Absorption Spectra ◽  
Oxidation State ◽  
Chlorine Atom ◽  
Reducing Agents ◽  
Ammonium Salts ◽  
Chlorine Atoms ◽  
Regular Triangle ◽  
New Compounds

The new compounds, K6Mo3IICl12; (NH4)7Mo3IICl13.H2O; and Cs6Mo4Cl16 (containing molybdenum in oxidation state +2.5) have been precipitated by the appropriate cation from solutions of molybdenum(II) acetate in 12M hydrochloric acid. The absorption spectra of potassium and ammonium salts are similar in the solid state and solution. Since the compounds are strong reducing agents and short-lived in solution, their formulation as a staphylonuclear (i.e. metal-clustered) trimer or tetramer rests on their diamagnetism, stoicheiometry, and spectral similarities. It is proposed that the chloromolybdates adopt entirely novel, compact polymers by stacking the chlorine atoms into "close packed" layers. The Mo3Cl13 group consists of two layers of chlorine atoms (seven and six) generating three octahedral locations for the molybdenum atoms at the corners of a regular triangle. The Mo3Cl12 group is similar but deficient in one chlorine atom. The Mo4Cl16 group is related to Mo3Cl13 and consists of three layers of chlorine atoms (seven, six, and three) providing four octahedral locations for the molybdenum atoms at the corners of a tetrahedron.

Chemistry of Fenchonesulfonic Acid Derivatives

1995 ◽  
Vol 50 (2) ◽  
pp. 283-288 ◽  
Author(s):  
Gabriele Wagner ◽  
Uwe Verfürth ◽  
Rudolf Herrmann
Keyword(s):  
Acetic Anhydride ◽  
Thionyl Chloride ◽  
Sulfonic Acid ◽  
Reaction Rate ◽  
Enantiomeric Excess ◽  
Methyl Group ◽  
Close Analogy ◽  
Chiral Sulfoxides ◽  
Mndo Calculations ◽  
Nmr Techniques

(1 S) - (+)-Fenchone is sulfonated by SO3 or H2SO4/acetic anhydride in the bridgehead methyl group. This could be confirmed by NMR techniques (INADEQUATE). The fenchonesulfonic acid obtained is converted (SOCl2/NH3) to the cyclic fenchonesulfonimide, which can be oxidized to the corresponding oxaziridine, in close analogy to 10-camphorsulfonimide. Improved procedures for this reaction sequences are given. During the treatment of the sulfonic acid with thionyl chloride, a byproduct with a rearranged bicyclic skeleton is observed whose structure has been determined by ozonolytic degradation and NMR techniques. A possible mechanism for this rearrangement is suggested, based on MNDO calculations of the intermediate carbocations. The fenchonesulfonyloxaziridine oxidizes sulfides to chiral sulfoxides with appreciable enantiomeric excess, but very low reaction rate. A comparison with camphor-derived oxaziridines having similar steric requirements is made.

Reaction Rate of Hydrogen Chloride and Sulfide with Steel

1945 ◽  
Vol 37 (11) ◽  
pp. 1092-1097 ◽  
Author(s):  
Carl F. Prutton ◽  
David Turnbull ◽  
George Dlouhy
Keyword(s):  
Hydrogen Chloride ◽  
Reaction Rate

The thermal decomposition of methylene chloride

1959 ◽  
Vol 250 (1261) ◽  
pp. 180-196 ◽  
Keyword(s):  
Thermal Decomposition ◽  
Hydrogen Chloride ◽  
Methylene Chloride ◽  
Flow System ◽  
Vessel Diameter ◽  
Chlorine Atoms ◽  
System A ◽  
Pressure Time ◽  
A Chain ◽  
Kinetic Features

The thermal decomposition of methylene chloride has been studied in the temperature range 500 to 650 °C by both the static technique of pressure-time measurement and the use of a flow system in conjunction with gas chromatographic analysis. The reaction, which leads principally to carbon and hydrogen chloride is characterized by a slow acceleration, the rate of which decreases with the vessel diameter. In vessels of diameter less than 5 mm the reaction is almost completely inhibited. The reaction rate is increased by the addition of inert gas, nitric oxide and, particularly, by dichlorethylene. Using the flow system a number of chlorinated hydrocarbons were detected as minor products of the reaction and their rate of formation relative to the major products was followed in detail. By identifying some of these as radical recombination products and one, dichlorethylene, as a degenerate branching agent, a delayed branching mechanism has been deduced which explains most of the kinetic features of the reaction as well as the formation of the observed minor products. This involves the production of the intermediate, dichlor­ethylene, in a chain carried by chlorine atoms and dichlormethyl radicals, and the conversion of this to carbon and hydrogen chloride by a coupled chain also involving chlorine atoms. The average primary chain length has been estimated as fifteen by measurement of the rate of formation of the supposed recombination products, but this figure is uncertain since the termination products appear to be destroyed in turn by chlorine atoms generated in the main chain.

Die Kristallstrukturen von PPh4[WOCl4], (PPh4)2[WOCl5] · 2CH2CI2 und (PPh4)2[ReOCl5] · 2CH2Cl2 / The Crystal Structures of PPh4[WOCl4], (PPh4)2[WOCl5] · 2CH2CI2 and (PPh4)2[ReOCl5] · 2CH2Cl2

1984 ◽  
Vol 39 (7) ◽  
pp. 850-854 ◽  
Author(s):  
Dieter Fenske ◽  
Karlheinz Stahl ◽  
Evamarie Hey ◽  
Kurt Dehnicke
Keyword(s):  
Oxygen Atom ◽  
Chlorine Atom ◽  
Complex Space ◽  
Unit Cell ◽  
Axial Position ◽  
Formula Unit ◽  
Tetragonal Pyramid ◽  
Space Group ◽  
Oxygen Ligand ◽  
Oxygen Distance

Both tungsten compounds are formed by reaction of water and oxygen with the acetylene complex PPh4[WCl5(Ph - C ≡ C - C (Br) = C(Br) -Ph)] in CH2Cl2 solutions, and in the presence of PPh4Cl. PPh4[WOCl4] crystallizes in the tetragonal space group P4/n, with two formula units in the unit cell of dimensions a = b = 1269, c = 760 pm at -110 °C (1416 observed in dependent reflexions, R = 0 .054). The [WOCl4]⊖ ion forms a tetragonal pyramid with the oxygen ligand in axial position and a tungsten -oxygen distance of 168 pm. (PPh4)2 [WOCl5 · 2CH2Cl2 crystallizes in the tricline space group P 1̄, with one formula unit per unit cell with a = 1011, b = 1113, c = 1240 pm, α = 70.3°, β = 79.4°, γ = 80.9° at - 110 °C (3781 observed in dependent reflexions, R = 0 .087). The structure contains [WOCl5]2⊖ an ions where the oxygen atom and the chlorine atom in transposition are disordered. (PPh4)2[ReOCl5] · 2CH2Cl2 is formed by the reaction of ReCl5 with PPh4Cl in the presence of water. The compound is isotypic with the corresponding tungsten complex (space group P 1̄, Z = 1, a = 1006, b = 1109, c = 1239 pm , α = 7 0.5°, β = 79.6°, γ = 80.9° at -110 °C; 5436 observed in dependent reflexions R = 0 .050).

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