Reaction of 1,1-diphenylpropene with stannic chloride and hydrogen chloride

1978 ◽  
Vol 56 (15) ◽  
pp. 2093-2095 ◽  
Author(s):  
Stanley Bywater ◽  
Denis J. Worsfold
Keyword(s):  
Chloride Solution ◽  
Methylene Chloride ◽  
Stannic Chloride ◽  
Heat Of Reaction ◽  
Initial Formation ◽  
Free Ions ◽  
Electrical Conductances ◽  
Methylene Chloride Solution ◽  
Carbenium Ion ◽  
Equilibrium Amount

SnCl4 and HCl have been found to react with 1,1-diphenylpropene to form a small equilibrium amount of the diphenylethylcarbenium ion. No further reaction is detectable, and the equilibrium between the three reactants may be determined from the uv absorption of the ion. The electrical conductances of the solutions have also been measured. The results are consistent with the formation of the salt of this carbenium ion with the SnCl5− anion. The salt in the concentrations formed in these experiments (ca. 10−5–10−4 M) was nearly all dissociated into free ions in methylene chloride solution. The equilibrium constant for formation of the salt was 2.0 M−2 at −30 °C, and the dissociation constant into ions 4.4 × 10−4 M. The overall heat of reaction to the carbenium ion salt was 8.8 kcal, most of which is attributed to the initial formation of the undissociated salt.

COMPLEXES OF STANNIC CHLORIDE WITH AROMATIC HYDROCARBONS AND OXYGEN-CONTAINING DONORS IN SOLUTION

1964 ◽  
Vol 42 (7) ◽  
pp. 1555-1562 ◽  
Author(s):  
J. J. Myher ◽  
K. E. Russell
Keyword(s):  
Complex Formation ◽  
Aromatic Hydrocarbons ◽  
Chloride Solution ◽  
Methylene Chloride ◽  
Ethyl Esters ◽  
Optical Measurements ◽  
Stannic Chloride ◽  
Heat Of Reaction ◽  
Donor Molecule ◽  
Methylene Chloride Solution

Complex formation between stannic chloride and various alkylbenzenes has been investigated by means of optical measurements. It is found that weak 1:1 complexes are formed in methylene chloride solution at 25 °C. The absorption at 355 mμ can be used to determine the concentration of free stannic chloride in benzene to which oxygen-containing donors have been added. The results are interpreted in terms of 1:1 and 1:2 complex formation between stannic chloride and donor. For the stronger donors such as tetrahydrofuran and acetone, the main complexes formed with excess of stannic chloride must contain equimolar amounts of stannic chloride and donor, and it is probable that they involve tin with a coordination number of five. Ethyl esters of chloroacids are very much weaker donors than ethyl esters of unsubstituted acids. The heat of reaction for the addition of a donor molecule to the 1:1 complex is usually close to the heat of reaction for the addition of the first donor molecule to stannic chloride. The decrease in entropy in each case is approximately 30 e.u./mole.

The addition of 2,4-dinitrobenzenesulphenyl chloride to 1,3-disubstituted allenes: a reexamination

1979 ◽  
Vol 57 (1) ◽  
pp. 119-127 ◽  
Author(s):  
Dennis G. Garratt ◽  
Pierre Beaulieu
Keyword(s):  
Double Bond ◽  
Chloride Solution ◽  
Methylene Chloride ◽  
Effective Mechanism ◽  
Substituent Group ◽  
Methylene Chloride Solution ◽  
Inductive Effects ◽  
Allene System

The reaction of 2,4-dinitrobenzenesulphenyl chloride with eight alkyl 1,3-disubstituted allenes in methylene chloride solution has been investigated. In contrast to earlier reports, attack by sulphur is found to occur exclusively at the central allenic carbon. The direction of approach of sulphenyl chloride leads preferentially to the formation of the E isomers in accord with the concept of steric approach control. The ratio of E to Z alkene is found to increase as the bulk of the substituent group cis to the arylthio group increases. We observe, however, very little regioselectivity with respect to which of the mutually perpendicular π bonds of the allene system is attacked, suggesting the presence of an effective mechanism for transmission of inductive effects to the more distant double bond.

The reactions of [Pd2Cl2(μ-PP)2] (PP = dppm, dmpm) with Et2NC≡CNEt2 in methylene chloride solution: X-ray crystal structures of [Pd2Cl2(μ-CH2)(μ-dppm)2] and hexakis(diethylamino)benzene, C6(NEt2)6

1996 ◽  
Vol 74 (11) ◽  
pp. 2331-2339 ◽  
Author(s):  
Sean R. Klopfenstein ◽  
Constanze Kluwe ◽  
Kristin Kirschbaum ◽  
Julian A. Davies
Keyword(s):  
Key Words ◽  
Crystal Structures ◽  
Chloride Solution ◽  
Methylene Chloride ◽  
X Ray ◽  
Methylene Chloride Solution ◽  
Methylene Group

The binuciear palladium(I) complex, [Pd2Cl2(μ-dppm)2] (dppm = bis(diphenylphosphino)methane), has been shown to react with bis(diethylamino)acetylene, Et2NC≡CNEt2, in methylene chloride solution to yield two isolable products, the known methylene-bridged complex, [Pd2Cl2(μ-CH2)(μ-dppm)2], and hexakis(diethylamino)benzene, C6(NEt2)6, both of which have been characterized crystallographically. The source of the bridging methylene group in [Pd2Cl2(μ-CH2)(μ-dppm)2] has been shown to be the methylene chloride solvent. A mechanism that accounts for the formation of the two isolable products is proposed. The complex, [Pd2Cl2(μdmpm)2] (dmpm = bis(dimethylphosphino)methane), was similarly found to react with Et2NC≡NEt2 in methylene chloride solution to yield [Pd2Cl2(μ-CH2)(μ-dmpm)2], which was identified spectroscopically. Key words: acetylene, palladium, cyclooligomerization, aminoacetylene, hexakis(diethylamino)benzene.

Nuclear magnetic resonance studies of ketone.BF3 complexes. I. Exchange reactions in methylene chloride solution

1968 ◽  
Vol 46 (12) ◽  
pp. 2147-2157 ◽  
Author(s):  
R. J. Gillespie ◽  
J. S. Hartman
Keyword(s):  
Chloride Solution ◽  
Methylene Chloride ◽  
Chemical Exchange ◽  
Exchange Process ◽  
Exchange Reactions ◽  
Methylene Chloride Solution ◽  
Donor Acceptor ◽  
Group 3 ◽  
Proton Resonances ◽  
Increasing Temperature

1H and 19F n.m.r. studies of BF3 adducts of some simple methyl ketones in methylene chloride solution have led to the following conclusions. (1) Only 1:1 adducts are formed which are not appreciably dissociated. (2) The down-field shifts of the proton resonances caused by complexation with BF3 are essentially independent of the ketone and depend only on the distance of the proton from the carbonyl group. (3) BF3 exchange is rapid on the n.m.r. time scale at room temperature, but the exchange process can be slowed sufficiently by lowering the temperature that separate signals due to free and complexed species can be observed. (4) Collapse of the 10B−11B isotope shift with increasing temperature showed that a second chemical exchange process, which exchanges fluorine among boron atoms, occurs in addition to the process of rapid breaking and re-forming of donor–acceptor bonds. A possible mechanism for this fluorine scrambling reaction is discussed.

The reaction of some propargyl alcohols with benzeneselenenyl chloride

1981 ◽  
Vol 59 (6) ◽  
pp. 927-934 ◽  
Author(s):  
Dennis G. Garratt ◽  
Pierre L. Beaulieu ◽  
Veronique M. Morisset
Keyword(s):  
Chloride Solution ◽  
Methylene Chloride ◽  
Kinetic Control ◽  
Methylene Chloride Solution ◽  
Propargyl Alcohols

The reaction of benzeneselenenyl chloride with twenty-two propargyl alcohols in methylene chloride solution is reported. Products of both Markownikoff and anti-Markownikoff regiochemistry are formed in an anti stereospecific manner. The regioselectivity or specificity is found to be very dependent upon the nature of the substituents geminal to the alcoholic moiety. In general the presence of bulky substituents geminal to the alcoholic moiety tend to favour formation of the anti-Markownikoff adduct under conditions of kinetic control. The Markownikoff adducts are found to be favoured thermodynamically.

Fluxional Behavior of a Cadmium Zwitterion Complex:  Proton Transport and Tautomerism in Methylene Chloride Solution

2003 ◽  
Vol 42 (15) ◽  
pp. 4513-4515 ◽  
Author(s):  
Oren P. Anderson ◽  
Agnete la Cour ◽  
Andrew Berg ◽  
Andrew D. Garrett ◽  
Mark Wicholas
Keyword(s):  
Proton Transport ◽  
Chloride Solution ◽  
Methylene Chloride ◽  
Methylene Chloride Solution

Synthesen und Kristallstrukturen von Tris(di-n-propylamino)-p-brombenzylphosphonium-bromiden: [(C3H7)2N]3PCH2C6H4Br+Br- und [(C3H7)2N]3PCH2C6H4Br+Br3-/Syntheses and Crystal Structures of Tris(di-n-propylamino)-p-bromobenzyl-phosphonium Bromides: [(C3H7)2N]3PCH2C6H4Br+Br- and [(C3H7)2N]3PCH2C6H4Br+Br3-

1999 ◽  
Vol 54 (1) ◽  
pp. 113-116 ◽  
Author(s):  
J. Nolte ◽  
P. Neubauer ◽  
H. Vogt ◽  
M. Meisel
Keyword(s):  
Crystal Structures ◽  
Chloride Solution ◽  
Methylene Chloride ◽  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
Methylene Chloride Solution

Tris(di-n-propylamino)-p-bromobenzylphosphonium bromide [(C3H7)2N]3PCH2C6H4Br+- Br- (1) has been prepared by the reaction of tris(di-n-propylamino)phosphine with p-bromobenzylbromide in methylene chloride. The colorless crystals are monoclinic, space group P21, Z = 2, a = 930.2(3), b = 1501.2(3), c = 1093.5(2) pm, β = 105,97(4)°. The lattice contains Br- anions and [(C3H7)2N]3PCH2C6H4Br+ cations. [(C3H7)2N]3PCH2C6H4Br+Br- (2) has been obtained by treating 1 with equimolar quantities of elemental bromine in methylene chloride solution. The yellow-red crystals of 2 are triclinic, space group P1̄, Z = 2, a = 1069.5(3), b = 1267.7(7), c = 1273.7(3) pm, α= 87.27(3), β = 82,67, γ = 67.15°, and consist of [(C3H7)2N]3PCH2C6H4Br+ cations and linear Br3- anions. The three N atoms in the cations of 2 are planar.

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