The 9-decalyl and related cations. V. Generation of cis- and trans-2-t-Butyl-9-decalyl cations through π-routes by acetolysis

1978 ◽  
Vol 31 (4) ◽  
pp. 863 ◽  
Author(s):  
GE Gream ◽  
AK Serelis
Keyword(s):  
Acetic Acid ◽  
Significant Role ◽  
Ion Pairs ◽  
Side Chain ◽  
Rate Enhancement ◽  
Cationic Species ◽  
Hydride Shift ◽  
Butyl Group ◽  
Counter Ion ◽  
Cis And Trans

The synthesis and solvolytic behaviour (in buffered acetic acid) of 4- (5?-t-butylcyclohex-1'-enyl)but-1-yl p-nitrobenzenesulfonate (6) and 3- (cyclohex-1'-enylmethyl)-4,4-dimethylpentyl p-nitrobenzene-sulfonate (7) are described. Kinetic and product studies have shown that π-bond participation occurs in the acetolysis of both compounds. The rate enhancements, compared with saturated analogues, are c. 46 and 8290 for (6) and (7). The considerably greater rate enhancement observed for (7) is a manifestation of the 'gem-dialkyl' effect and is explained in terms of the effect of the t-butyl group on the conformations that the side chain might adopt. ��� The acetolyses of (6) and (7) give rise to cyclized products (c. 97 and 100%) arising from both cis- and trans-2-t-butyl-9-decalyl cations (2) and (3). The compositions of the products, which also include compounds formed from the cis-cation (55) obtained by a 1,2-hydride shift in (2), show that (6) and (7) do not react via the same cationic species. ��� Ion-pairs of an undefined nature are implicated in the reactions. Entirely consistent evidence was not obtained for the hypothesis that the counter-ion, behaving as a base, probably plays a significant role in olefin formation from the cis- and trans-cations (2) and (3) in ion- pairs that might be formed initially from (6) and (7).

The 9-decalyl and related cations. III. Generation of the 8-hydrindyl cation by solvolysis

1974 ◽  
Vol 27 (8) ◽  
pp. 1711 ◽  
Author(s):  
GE Gream ◽  
AK Serelis ◽  
TI Stoneman
Keyword(s):  
Ion Pairs ◽  
Cationic Species ◽  
Direct Route ◽  
Counter Ion ◽  
Product Composition ◽  
Cis And Trans

Acetolysis of 4-(cyclopent-1'-enyl)butyl and 3-(2'-methylenecyclopentyl)propyl derivatives, but not 3-(cyclohex-1'-enyl)propyl and 2-(2'-methylenecyclohexyl)ethyl derivatives, occurs with π-bond participation (95 and 92%, respectively) to give similar, including maybe identical, cationic species involving the 8-hydrindyl cation. On the basis of product composition, the 8-hydrindyl cations when generated from spiro[4,4]non-1-yl (σ-route) and cis- and trans-8-hydrindyl derivatives (direct route) are each different and are in turn different to those generated by the above π-routes. Reasons for the differences are discussed and the possible role of the counter-ion in ion-pairs is examined.

Adduct Intermediates in the Side-chain Nitration of 1,4-Dimethylnaphthalene

1972 ◽  
Vol 50 (24) ◽  
pp. 3988-3992 ◽  
Author(s):  
Alfred Fischer ◽  
Alan Leslie Wilkinson
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Acetic Anhydride ◽  
Room Temperature ◽  
Methylene Chloride ◽  
Side Chain ◽  
Trans Isomers ◽  
Cis And Trans Isomers ◽  
Cis And Trans ◽  
Naphthyl Acetate

cis and trans isomers of 1,4-dimethyl-4-nitro-1,4-dihydro-1-naphthyl acetate (1) have been isolated from a mixture of 1,4-dimethylnaphthalene and nitric acid in acetic anhydride by quenching at −40°. At room temperature only 1-methyl-4-nitromethylnaphthalene (4) is obtained. The conversion of 1,4-dimethylnaphthalene to 4 and of the cis (1a) and trans (1b) adducts to 4, by nitric acid in acetic anhydride, has been followed by n.m.r. 1,4-Dimethyl-4-nitro-1,4-dihydro-1-naphthyl nitrate (5) appears to be the immediate product from nitration of 1,4-dimethylnaphthalene in acetic anhydride, methylene chloride, or nitromethane. In acetic anhydride 5 is converted into 1. Decomposition of 1 in acetic acid gives 1,4-dimethyl-2-naphthyl acetate and some 4. The formation of 4 in this reaction is suppressed by urea.

The 9-decalyl and related cations. I. Generation of the 9-decalyl cation by solvolysis

1972 ◽  
Vol 25 (5) ◽  
pp. 1051 ◽  
Author(s):  
GE Gream
Keyword(s):  
Ion Pairs ◽  
Product Formation ◽  
Counter Ion ◽  
Quantitative Analyses ◽  
Cis And Trans

Kinetic and product studies have established that π-bond participation occurs in the acetolysis of 4-(cyclohex-1-enyl)but-1-yl derivatives to give a 9-decalyl cation. Quantitative analyses of the mixtures of products formed by the x-route (from 4-(cyclohex-1-enyl)but-1-yl derivatives), π-route (from spiro[4,5]dec-6-yl derivatives), and direct routes (from cis- and trans-9-decalyl derivatives) show that the intermediate 9-decalyl cations generated in each case must be different. Reasons for the differences are discussed; it is suggested that the counter-ion in ion-pairs involving cis-like and trans-like conformers of the 9-decalyl cation probably plays an important role in product formation.

Potential antitumor agents. 63. Structure-activity relationships for side-chain analogs of the colon 38 active agent 9-oxo-9H-xanthene-4-acetic acid

1991 ◽  
Vol 34 (9) ◽  
pp. 2864-2870 ◽  
Author(s):  
Gordon W. Rewcastle ◽  
Graham J. Atwell ◽  
Bruce C. Baguley ◽  
Maruta Boyd ◽  
Lindy L. Thomsen ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Antitumor Agents ◽  
Active Agent ◽  
Side Chain ◽  
Structure Activity Relationships ◽  
Structure Activity ◽  
Potential Antitumor

Cyclic side-chain-linked opioid analogs utilizing cis - and trans -4-aminocyclohexyl- d -alanine

2014 ◽  
Vol 22 (23) ◽  
pp. 6545-6551 ◽  
Author(s):  
Justyna Piekielna ◽  
Luca Gentilucci ◽  
Rossella De Marco ◽  
Renata Perlikowska ◽  
Anna Adamska ◽  
...  
Keyword(s):  
Side Chain ◽  
Cis And Trans

Octahedral cobalt(III) complexes in dipolar aprotic solvents. II. Association between cis- and trans-dichlorobisethylenediamine cobalt(III) cations,[Co en2 Cl2]+, and chloride and bromide ions in the solvents NN-dimethylformamide, dimethyl sulphoxide, and LVN-dimethylacetamide

1966 ◽  
Vol 19 (1) ◽  
pp. 43 ◽  
Author(s):  
WA Millen ◽  
DW Watts
Keyword(s):  
Spectrophotometric Method ◽  
Ion Pairs ◽  
Ion Association ◽  
Ion Pair ◽  
Association Constants ◽  
Dimethyl Sulphoxide ◽  
Aprotic Solvents ◽  
Ion Association Constants ◽  
Cis And Trans ◽  
Dipolar Aprotic Solvents

Ion association constants at 30� have been determined for the cis-[Co en, Cl2]+Cl- ion pair in NN-dimethylformamide (DMF), NN-dimethylacetamide (DMA), and at 20.0�, 25.0�, and 30.0� in dimethyl sulphoxide (DMSO), by a spectrophotometric method. Association constants for the cis-[Co en2 Cl2]+Br- and the trans- [Co en2 Cl2]+Cl- ion pairs have also been determined in DMF at 30�.

scholarly journals On active chlorine

1934 ◽  
Vol 147 (861) ◽  
pp. 309-332
Keyword(s):  
Acetic Acid ◽  
Electric Discharge ◽  
Closed System ◽  
Surface Characteristics ◽  
Chemical Activity ◽  
Active Chlorine ◽  
Side Chain ◽  
Experimental Conditions ◽  
Electrically Charged ◽  
Atomic Chlorine

Evidence has long been available that a modification of chlorine of abnormal chemical activity is produced by an electric discharge in this gas. The greater part of the earlier work was conducted under very badly defined experimental conditions which render the various researches difficult to correlate, but the properties of this “active chlorine” may be summarized as follows:— ( a ) It possesses abnormal bleaching powers, and can react in the cold and the dark with acetic acid to form the monochlor derivative; with benzene it gives the hexachloride, while with toluene the combination occurs mainly in the side chain. ( b ) They yield of active gas is enhanced by irradiation of the discharge, by cooling, and by the presence of moisture. ( c ) It has a life period of at least 75 secs, but is destroyed by heating, passage through water, and the action of another discharge; it is not electrically charged and does not possess as abnormal density.§ ( d ) Since only very small changes in pressure follow passage of a discharge in a closed system containing chlorine, the active modification does not presumably represent an associated molecule such as Cl 3 .‖ Reference may also be made to papers by Venkataramaiah¶ who gives a number of chemical reactions of chlorine activated in various ways but his results must be treated with reserve (see Germann, idem ., p. 951). In the present experiments we have endeavoured to repeat and extend the earlier studies under better defined conditions, and conclude that the phenomena are very probably due to a trace of atomic chlorine whose behaviour is markedly dependent upon the surface characteristics of the apparatus.

Structural studies on monofluorinated derivatives of the phytohormone indole-3-acetic acid (auxin)

1996 ◽  
Vol 52 (4) ◽  
pp. 651-661 ◽  
Author(s):  
A. Antolić ◽  
B. Kojić-Prodić ◽  
S. Tomić ◽  
B. Nigović ◽  
V. Magnus ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Side Chain ◽  
Structural Studies ◽  
X Ray Diffraction ◽  
Molecular Conformations ◽  
X Ray ◽  
Structure Activity ◽  
Planar Conformation ◽  
Derivatives Of ◽  
Indole 3 Acetic Acid

As part of the molecular recognition studies on the phytohormone indole-3-acetic acid (IAA) a series of fluorinated IAA's has been examined. The phenyl ring substitution at positions 4, 5, 6 and 7 resulted in four compounds, which were analyzed. Structure–activity correlation includes the analysis of their molecular conformations, based on the X-ray diffraction and computational chemistry results, and bioactivity determinations in the Avena coleoptile and the Pisum sativum stem straight-growth tests, lipophilicity and UV absorbance. The conformations of monofluorinated IAA's and a free hormone are defined by rotations about two bonds: one describes the relative orientation of a side chain towards the indole plane and the second the orientation of the carboxylic group. The results of X-ray structure analysis revealed the folded shape of the molecules in all compounds studied. Molecular mechanics and dynamics located the folded conformation as the local minimum, but failed to detect the planar conformation as one of the local minima, which according to ab initio results on IAA and 4-CI-IAA could also be possible. Crystal data at 295 K for 4-F-IAA and at 297 K for 5-F-IAA, and at 100 K for 6-F-IAA and 7-F-IAA using Mo Kα radiation (λ = 0.71073 Å) and Cu Kα (λ = 1.5418 Å, for 7-F-IAA), are as follows: 4-F-IAA, C10H8NO2F, Mr = 193.18, monoclinic, C2/c, a = 17.294 (5), b = 13.875 (4), c = 7.442 (4) Å, β = 103.88 (6)°, V = 1734 (1) Å3, Z = 8, Dx = 1.480 g cm−3, μ = 1.1 cm−1, F(000) = 800, R = 0.043, wR = 0.044 for 823 symmetry-independent [I ≥ 3σ(I)] reflections; 5-F-IAA, C10H8NO2F, monoclinic, P21/c, a = 19.284 (5), b = 5.083 (4), c = 9.939 (4) Å, β = 117.28 (6)°, V = 865.9 (1) Å3, Z = 4, Dx = 1.482 g cm−3, μ = 1.1  cm−1, F(000) = 400, R = 0.062, wR = 0.057 for 729 symmetry-independent [I ≥ 3σ(I)] reflections; 6-F-IAA, C10H8NO2F, monoclinic, P21/a, a = 9.360 (1), b = 5.167 (4), c = 17.751 (4) Å, β = 93.75 (1)°, V = 856.7 (8) Å3, Z = 4, Dx = 1.498 g cm−3, μ = 1.1 cm−1, F(000) = 400, R = 0.048, wR = 0.048 for 1032 symmetry-independent [I ≥ 2σ(I)] reflections; 7-F-IAA, C10H8NO2F, monoclinic, P21/a, a = 9.935 (5), b = 5.0059 (4), c = 17.610 (1) Å, β = 102.13 (1)°, V = 856.3 (1) Å3, Z = 4, Dx = 1.498 g cm−3, μ = 9.8 cm−1 (Cu Kα, F(000) = 400, R = 0.035, wR = 0.040 for 1504 symmetry-independent [I ≥ 2σ(I)] reflections.

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