Stereoselectivity in the reductive cleavage of vinylcyclopropane

Treatment of vinylcyclopropane (6) with lithium in liquid ammonia at 0° or 25° slowly effects reductive cleavage to afford a mixture of cis-2-pentene (7), trans-2-pentene (8), and 1-pentene (9). The major product is 7 and the ratio 7:8 is greater at 0° (4·25) than at 25° (3·2). Control experiments have established that the products are stable in lithium amide-liquid ammonia at 25°. In contrast, product ratios for cleavage of 6 with sodium in liquid ammonia at 0° or 25° are somewhat variable due to equilibration under the reaction conditions, and 8 is the major product at longer reaction times at 25°. It is suggested that the predominant cis-stereoselectivity is greatest in solvent-separated ion pair transition states.     

The synthesis of cypridina etioluciferamine and the proof of structure of cypridina luciferin

An unambiguous synthesis of Cypridina etioluciferamine was accomplished in order to prove the structure of this important bioluminescent natural product. Several 2-aminopyrazine 1-oxides were synthesized in order to establish a spectroscopic method for determining the placement of substituents on the pyrazine nucleus of Cypridina etioluciferamine. Titanium tetrachloride was used to improve the yields of these compounds; for example, the yield of 2-amino-3-methyl-5-phenylpyrazine 1-oxide (19) from reaction of phenylglyoxal 1-oxime and α-aminopropionitrile was raised from 3% to 51% by the use of titanium tetrachloride. The pyrazine ring proton is found at τ 1·37 (DMSO-d₆). The isomeric 2-amino-3-methyl-6-phenylpyrazine 1-oxide (22) was similarly prepared and its pyrazine ring proton is found at τ 2·18. This large difference (0·81 ppm) in chemical shift was used to determine whether a 2-aminopyrazine 1-oxide was 5- or 6- substituted. Prepared in an analogous fashion were 2-amino-5-(indol-3-yl)-3-methylpyrazine 1-oxide (23) and 2-amino-5-(indol-3-yl)-3-(3-phthalimidopropyl)pyrazine 1-oxide (16). The structures of these compounds were verified by NMR spectroscopy. By treatment with Raney nickel and hydrogen gas, then 100% hydrazine hydrate, 16 was converted to 2-amino-3-(3-aminopropyl)-5-indol-3-ylpyrazine (5), isolated as the dihydrochloride. This compound, with the indole moiety definitely placed at C-5, is identical with Cypridina etioluciferamine dihydrochloride (IR, UV, TLC). These results show that the structures of Cypridina etioluciferamine and luciferin are correct as published.     

Base-induced rearrangements of 3-(α-haloacyl)indoles : A convenient route to indole-3-acetic acids and tryptopholes

Base-induced reactions of 3-(α-haloacyl)indoles have been investigated. Rearrangement is a general reaction observed under the influence of various bases, e.g. hydroxide, hydride and Grignard reagent. Indole-3-acetic acids (20–32) are formed in fair yields when the reaction is performed with sodium hydroxide in 80% aqueous ethanol. The carbon monoxide evolved during the reaction appears to be eliminated from an intermediate cyclopropanone (33). Tryptopholes (53–55) are prepared in good yields by LiAlH₄-reduction of 3-(α-haloacyl)indoles.     

Kinetik und mechanismus der epoxidierung von allylalkohol mit peroxykomplexen des molybdäns (VI)

The kinetics of the allylalcohol epoxidation by peroxycomplexes MoO(O₂₂L₁L₂ (1) and MoO(O₂)₂L₁ (2), where L₁=hexamethylphosphotriamide, L₂ = H₂O, has been studied in 1,2- dichlorethane within the 30–60°C temperature range. The reaction-rate observed by the oxygen content decreased is directly proportional to the concentration of both complexes. The reaction rate dependence on the allylalcohol concentration is described by the Michaelis-Menten equation. The parameters of this equation were determined at 50°C. K_m is equal to 0·78 and 0·81 Mol/l for 1 and 2 respectively. The activation energy values are 16·1 ± 0·5 and 18·3 ± 1·0 Kcal/Mol for 1 and 2, respectively. The glicidol yield at 50°C is varying from 70 to 100% for 2 and from 65 to 75% for 1 depending on the convertion level of the reaction. The epoxidation mechanism of allylalcohol by covalent molybdenum (VI) peroxy-complexes is discussed.     

Relative reactivities of bicyclo[3.2.1]octa-2,3-diene and 1,2-cycloheptadiene with conjugated dienes and styrene

Bicyclo[3.2.1]octa-2,3-diene (2) and 1,2-cycloheptadiene (3), generated by treatment of the corresponding dichlorides 4 and 5 with magnesium, were found to undergo cycloaddition reactions with 2,3-dimethylbutadiene, styrene, and 1,3-cyclopentadiene. 2, but not 3, was also found to undergo a (2 + 2) cycloaddition reaction with cis-pentadiene. The relative reactivities of 2 and 3 with cis-pentadiene, 2,3-dimethylbutadiene, styrene, and 1,3-cyclopentadiene at 60° in THF were found to be: 0·18, —; 1·0, 1·0; 0·60, 7·5; and 4·0, 150.     

Synthesis of pinacol esters of 2,3-alkadienylboronic acid via the copper(I) mediated coupling reaction of Knochel's (dialkoxyboryl)methylzinc reagents with propargylic tosylates

The reaction of propargyl tosylates (1) with (dialkoxyboryl)methyl-copper(I) reagents, prepared in situ from Knochel's (dialkoxyboryl)-methylzinc iodide (2) and CuCN · 2LiCl, produced 2,3-alkadienyl-boronates (3) in moderate yields. The reaction proceeded regioselectively to provide an S_N2' substitution product without contamination by other products such as 3-alkynylboronate.     

Crystal structures and physicochemical properties of mixed salts of ammonium nitrate and sulfate

Mixed salts (NH₄)₂SO₄·2NH₄NO₃ (1) and (NH₄)₂SO₄·3NH₄NO₃ (2) were synthesized and studied by X-ray diffraction analysis. The unit cell parameters of these salts were determined and their crystal structures were solved. The thermal stability of the salts was studied by differential scanning calorimetry and thermogravimetric analysis. The temperatures and enthalpies of incongruent melting of compounds 1 and 2 were determined. The enthalpies of formation from the constituent salts were estimated.     

New evidence for and new reactions of ortho-lithio ylids

While α-lithio ylid 2 my be generated from triphenylphosphonio-bromomethylid through halogen/metal exchange, the reaction of triphenyl phosphonio-methylid 1 with sec- or tert-butyllithium produces nearly quantitatively the o-lithio ylid 3 , which is stable at -60° but slowly decomposes at higher temperatures via a cyclization product 5 to give the α-lithio phosphine 4.     

The asymmetric synthesis of cyclopentane derivatives by palladium-catalyzed coupling of prochiral alkylboron compounds

Treatment of the prochiral triflate 2a with Pd₂(dba)₃·CHCl₃, (S)-(R)-BPPFOAc and K₂CO₃, in THF at 40°C, gave the cyclopentane derivative 10 in 58% yield and in 28% ee after oxidative work-up and benzoylation. Moreover, reaction of the prochiral triflate 2c with Pd₂(dba)₃·CHCl₃, (S)-(R)-PPFA and K₂CO₃, in THF at 40°C, afforded the cyclopentane derivative 3b, with a quaternary carbon center, in 42% yield and in 31% ee after oxidative work-up.     

Metal π complexes of benzene derivatives: Part 56. (η6-Fluoranthene)(tricarbonyl)chromium: isomerism and haptotropic equilibration

Reaction of fluoranthene with Cr(CO)₃Py₃/BF₃·OEt₂ at 25 °C affords a mixture of two isomeric complexes: traces of tricarbonyl(1-5,15-η⁶-fluoranthene)chromium (3) (coordination to benzene) and, as the major product, tricarbonyl(1-4,15,16-η⁶-fluoranthene)chromium (2) (coordination to naphthalene). The ratio 3:2 is less than 0.05 according to ¹H-NMR of crude product before crystallization. Complex 2 is thermodynamically less stable than 3: at 100 °C in decane or C₆D₆ for 8 h or at 90 °C in C₆F₆ for 100 h 2 rearranges irreversibly to 3 via an inter-ring haptotropic shift of the Cr(CO)₃ group from the naphthalene moiety to the benzene part of the fluoranthene ligand. NMR evidence for a degenerate reversible haptotropic shift within the naphthalene moiety is absent. The isomers 2 and 3 have been characterized by X-ray structural analysis.     

Decomposition of diacyl peroxide—VII : Oxygen scrambling in 1-apocamphoryl peroxide and related diacyl peroxides-general remarks on the relationship between the stability of acyloxy radical and amounts of cage recombinations and ester formation in the decomposition of diacyl peroxide

Thermal decomposition of 1-apocamphoryl peroxide has been investigated in CCl₄ using the ¹⁸O-labelled peroxide. 1-Apocamphoryl peroxide is the first example which undergoes radical decomposition, carboxy-inversion and oxygen scrambling reaction between carbonyl and peroxidic O atoms in the peroxide in comparable rates. The major product of the decomposition was the inversion product, 1-apocamphoryl 1-apocamphyl carbonate (52·5%), and only a minute amount of 1-apocamphyl 1-apocamphorate (2·2%) was formed. The rates of oxygen scrambling were found to be 2·70±0·21 × 10^?6 (55°), 1·85±0·12 × 10^?1 sec^?1 (70°) and 9·33±0·18 × 10^?5 sec^?1 (84·3°) (E_a, 27·5 Kcal/mol, ΔS3, ?2·3 e.u.). The cage recombination mechanism was suggested for the oxygen scrambling and the amounts of cage recombination of 1-apocamphoryloxy radical pair were calculated as 65% (55°), 60% (70°) and 52% (84·3°). The yield of the ester and the amount of cage recombination of geminate acyloxy radical pair were rationalized in terms of the stability of acyloxy radicals formed in the cage.     

Benzoxadiazocines,benzothiadiazocines and benzotriazocines-IV : Ring closure of 1-(2-[n-(2-chloroethyl and 2-hydroxyethyl)-n-methylamino]phenyl)-3-phenylthioureas. tetrahydroquinoxaline vs.dihydro-3,1,6-benzothiadiazocine and hexahydro-1,3,6-benzotriazocinethione formation

While base induced ring closure of 1-(2-[N-(alkylsulfonyl and arylsulfonyl)-N-(2-chloroethyl)amino]phenyl)-3-phenylthioureas 1 had furnished the corresponding type 2 dihydro-3,1,6-benzothiadiazocine derivatives rather than the isomeric hexahydro-1,3,6-benzotriazocinethiones (3) or tetrahydroquinoxalines (4), base induced ring closure of the related N-(2-chloroethyl)-N-Me derivatives 9a-9c, 10a and lOb furnishes type 14 tetrahydroquinoxalines. 14a is obtained also by treating the N-(2-hydroxyethyl)-N-Me derivative 11 with the triphenylphosphine-diethyl azodicarboxylate (DEAD) reagent. In situ replacement of the chlorine atom of compound 9a by iodine in the absence of base as well as treatment of 1-(2-[N-(2-hydroxyethyl)-N-methylamino]phenyl)-1-methyl-3-phenylthiourea (18) with the triphenyl-phosphine-DEAD reagent furnishes the benzimidazole derivatives 16 and 22, respectively, whose formation may be rationalised by assuming the intermediacy of the dihydro- and tetrahydro-3,1,6-benzothiadiazocine derivatives 12a · HI and 20, respectively, and their subsequent ring contraction.     

Stereoselective conjugate addition of TMSI-activated butylcopper to 1-(R)-endo-(1-naphthyl)bornyl crotonate

Conjugate addition of butylcopper/iodotrimethylsilane to naphthylbornyl crotonate (1) at −60°C gives 1-[1-(R)-endo-(1-naphthyl)]bornyl [(S)-3-methyl]-heptanoate (2) in 93% yield and 98% diastereomeric excess. The addition of TMSI-activated butylcopper is faster at −60°C than that of lithium dibutylcuprate (LiBu₂Cu).     

Synthetic and structural studies of [6]-, [7]- and [10]metacyclophanes

A new preparative sequence from 2,3-polymethylene-2-cyclopentenone 5 to 2,6-polymethylenebromobenzenes 3 (n = 6, 7, 10) and 2,6-polymethylenephenyllithiums 6 has been found. The reaction of 6 with various electrophiles produces a number of new compounds to disclose the unique reactivity of the aryl C-Li moiety surrounded by the polymethylene chain. Photolysis of 3a and 3b provides transannular products 8, 10 and 11, all arising from the proximity between the aromatic bromine and the aliphatic hydrogen intraannularly opposed to be removed as HBr. Spectrometric study gives quantitative data of the dependence of the molecular geometry upon the chain length and the aromatic substituents. The energy barriers ΔG_c^≠ of the conformational flipping are 17·4 kcal/mol (T_c 76·5°) for [6]metacyclophane (7a), 11·5 kcal/mol (T_c ?28°) for [7]metacyclophane (7b), ·8 kcal/mol for [10]metacyclophane (7c). The lower-energy process of the aliphatic chain in [6]metacyclophane derivatives is the pseudorotation with substituent-dependent barrier ΔG_c^≠ 11·1 kcal/mol (T_c ?31·5°) for 7a, 12·4 kcal/mol (T_c ?4·5°) for 3a and 12·7 kcal/mol (T_c 1·0°) for 12a. The rather large rotational barrier is attributed to the compressed structure of each system. The benzene ring distortion of the cyclophanes is deduced from the bathochromic shift of the B-band and the diamagnetic shift of the benzene proton signals in the PMR.     

Reaction of 5,5-diphenyl-2-thiohydantoin with 1,3-dibromopropane : Crystal and molecular structure of 2,3,4,5-tetrahydro-6,6-diphenylimidazo [2, 1-b]-thiazine-7 (6H)-one

The reaction between the potassium salt of 5,5-diphenyl-2-thiohydantoin (1) and 1,3-dibromopropane carried out in DME under anhydrous conditions has been found to give two isomeric diphenylimidazothiazines 2 and 3. When the reaction of 1 with 1,3-dibromopropane was performed in protic solvents (EtOH, HOH, NaOH) 2 and 3-(3-mercaptopropyl) - 5,5 - diphenylthiohydantoin (4) were formed. The latter is the product of hydrolysis of 3 taking place under the reaction conditions. 2,3,4,5 - Tetrahydro - 6,6 - diphenylimidazo [2,1-b] - thiazine - 7 (6H) - one (2) crystallises in space group P2₁/n with a =10.812(3), b =14.905(7), c =9.885(4) Å, β = 104.91(2)°. The 5-membered ring in 2 is planar whereas the 6-membered thiazine ring adopts the sofa conformation.     

Skipped diynes—VII : Stereospecific thermal isomerization of a tetraethynyldimethylenecyclobutane

1,1-Bis(t-butylethynyl)-3-t-butylchloroallene (1) dimerizes stereospecifically at ca 25° to give Z - 1 - (t - butylchloromethylene) - 2- bis(t - butylethynylmethylene) - 3 - t - butyl - 3 - chloro - 4,4 -bis(t - butylethynyl)cyclob Z-I in the solvent bis(2 - ethoxyethyl) ether. Rate data for 100° are k = 111 × 10^?6 sec^?1, ΔH^≠ = 30·8 ± 1 kcal/mole and ΔS^≠ = 15 ± 3 eu. It is proposed that the dimerization of 1 produces a bisallyl diradical in an orthogonal conformation from which conrotatory paths lead to Z-I or trans-II. The observations on this system are used to construct a useful, if simplistic, approach to rationalize or predict product distributions in reactions such as allene dimerizations, 1, 2 - dimethylenecyclobutane rearrangements, etc, which proceed through the bisallyl diradical. On the graph which connects all of the species (or on the energy surface which contains all of the species) the first products should be those which are one allowed reaction step away from a given diradical. Applications and exceptions to this concept of favored kinetic control are discussed.     

IR spectra and thermal decomposition/dehydration of double complex salts of lanthanum(III) sulphate complex anions with several cobalt(III) ammine complex cations

Double complex salts of lanthanum(III) sulphate complex anions with several cobalt(III) ammine complex cations, [Co(NH₃)₆][La(SO₄)₃]·H₂O (1), (NH₄)₃[Co(NH₃)₅ H₂O]-[La(SO₄)₃]₂·2H₂O (2), and (NH₄)₃[Co(NH₃)₄(H₂O)₂][La(SO₄)₃]₂·2H₂O (3), were prepared by the addition of hexaamminecobalt(III), pentaammineaquacobalt(III), and cis- tetra-amminediaquacobalt(III) complexes to the solution containing lanthanum(III) ion and excess ammonium sulphate. The IR spectra of sulphate groups of these double complex salts were much more complicated than those of the almost free sulphate groups such as (NH₄)₂SO₄ and [Co(NH₃)₆]₂(SO₄)₃·5H₂O. Furthermore, values of activation energy in the dehydration process of 1, 2 and 3 were estimated using modified Doyle's and Wiedemann's method. They were 95.6 ± 4.3, 157.1 ± 15.5 and 163.2 ± 20.8 kJ mol^?1, respectively. Here, one molecule water is released per molecule of 1, 2 and 3.     

Comprehensive comparison between the reaction of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>'-cyclohexane-1,2-diylidene-bis(4-methoxybenzoylhydrazide) with mercury(II) and copper(II) ions. Synthesis,structure, and kinetics of complex formation

Comprehensive comparison between the reaction of N,N'-cyclohexane-1,2-diylidene-bis(4-methoxybenzoylhydrazide) (CHMBH) with HgCl₂ and Cu(NO₃)₂ · 2.5H₂O salts have been investigated, including the synthesis, structure and kinetic of complex formation. The reactions of CHMBH with HgCl₂ or Cu(NO₃)₂ · 2.5H₂O at the same synthetic conditions have been shown to produce completely different type of complexes: [Hg(CHMBH)Cl₂] · CH₃CN (I) and [Cu₃(μ₃-OH)(CTMB)₃(NO₃)₂(CH₃CN)₂] · 5CH₃CN · H₂O (II) (CTMB = cyclohexotriazole-3-(4-methoxybenzamide)). The prepared compounds were characterized using different techniques (NMR, IR, UV-Vis and mass spectroscopies, microelemental analysis, thermogravimetry as well as X-ray powder differection and X-ray single crystal crystallography for I (CIF file CCDC no. 1503398). X-ray crystallography shows that the isolated product of I is a mononuclear complex which contains the [Hg(CHMBH)]²⁺ core. While, the isolated product of II was a trinuclear Cu(II) cluster [Cu₃(μ₃-OH)(CTMB)₃(NO₃)₂(CH₃CN)₂] · 5CH₃CN · H₂O which contains three differently coordinated copper sites. Kinetic studies on the formation of I have been also investigated and compared with that of II. In case of I, the reaction was so slow and exhibits a first-order dependence on the concentration of metal salt and a first-order dependence on the concentration of CHMBH. While in II, the study shows that the reaction is fast and occurs in three distinct phases.     

Synthesis and structures of organoantimony and organobismuth derivatives of 4-sulfophenol and 2,4-disulfophenol

Tetraphenylbismuth 4-hydroxybenzenesulfonate (I) and tetraphenylantimony 4-hydroxybenzenesulfonate (II) are synthesized in yields up to 80% by the reaction of pentaphenylbismuth and pentaphenylantimony, respectively, with 4-sulfophenol. Compounds I and II are also prepared by the ligand redistribution reaction from pentaphenyl compounds of bismuth and antimony and triphenylbismuth bis(4-hydroxybenzenesulfonate) and triphenylantimony bis(4-hydroxybenzenesulfonate), respectively, in yields up to 87%. The recrystallization of compounds I and II from water gives crystalline hydrates Ph₄BiOSO₂C₆H₄(OH-4) · H₂O (III) and Ph₄SbOSO₂C₆H₄(OH-4) · H₂O (IV). Pentaphenylbismuth and pentaphenylantimony react with 2,4-disulfophenol in acetone, regardless of the ratio of the starting reactants, to form bis(tetraphenylbismuth) 4-hydroxybenzene-1,3-disulfonate (V) and bis(tetraphenylantimony) 4-hydroxybenzene-1,3-disulfonate (VI) in yields up to 74%. According to X-ray diffraction data, coordination of the bismuth atoms in compound I is trigonal-bipyramidal with the axial oxygen atom of the 4-hydroxybenzenesulfonate group (Bi···O 2.764 Å). In compound II, coordination of the Sb atom is tetrahedral (CSbC angles 106.2°–112.3°). In crystal III, the distances between the central atom and the nearest oxygen atoms of the arenesulfonate group and the hydrate water molecule are 3.094 and 3.125 Å, respectively. Crystals V and VI consist of doubly charged anions of 2,4-disulfophenol and several distorted tetrahedral cations of tetraphenylbismuthonium (CBi(1)C, CBi(2)C angles and Bi(1)-C, Bi(2)-C bond lengths vary in the intervals 102.1°–122.7°, 105.4°–114.0° and 2.103–2.230, 2.187–2.209 Å, respectively) and tetraphenylantimonium (CSb(1)C, CSb(2)C angles and Sb(1)-C, Sb(2)-C bond lengths 106.3°–112.2°, 101.3°–122.4° and 2.095–2.110, 2.092–2.123 Å, respectively). The Bi(1) and Sb(2) atoms are coordinated by one of the oxygen atoms of the 2,4-disulfophenol anions (distances Bi(1)···O(3) 2.803, Sb(2)···O(1), 2.704 Å).     

Synthesis of a new conformationally defined serotonin homologue by intramolecular [4+2] cycloaddition

Treatment of 1-[(p-methoxyphenyl)sulfonyl]-2-methyl-3-[N-allyl-N-methyl-3-(2,6-dichlorobenzoyl)propylamino]indole 3 with triethylamine in chlorobenzene at 135°C results in the formation of 1,2,3,4,4a,5,6,11c-octahydro-7-[(p-methoxypyhenyl)-sulfonyl]-3-methyl-7H-pyrido[3,4-c]carbazole 1b in 58% yield. The reaction is selective in giving predominantly the trans isomer.