Thermochemical properties of benzoic acid derivatives VIII. Enthalpies of combustion and formation of o-, m-, and p- t-butylbenzoic acids

The enthalpies of formation in the crystalline state at 298.15 K of o-, m-, and p-t-butyl-benzoic acids have been determined by static-bomb calorimetry. Vapour-pressure determinations were made by the Knudsen-effusion technique and the sublimation enthalpies at the mean temperatures of the measurement ranges have been derived for the three acids. The values obtained are:

     

862.

Massenspektren neuer Phloroglucide,insbesondere solcher mit Valerylseitenketten     

M. Lounasmaa  C.-J. Widn  T. Reichstein 《Helvetica chimica acta》1973,56(3):1133-1144

Mass spectra of phloroglucinol derivatives recently isolated from African Dryopteris species are presented. Phloroglucides with n-valeryl side chain were found in these ferns for the first time. In the mass spectra they show strong peaks corresponding to loss of propene (C₃H₆) produced by McLafferty rearrangement, as shown in model compounds. Aside of the rottleron change (discussed formerly) this must be considered in order to avoid wrong interpretation, particularly when mass spectra are used to analyse mixtures of homologues, as usually present in the plants. If valeryl side chains are present other methods must be used therefore to measure the amount or show the absence of lower homologues with acetyl side chains.     

863.

A kinetic approach to homogeneous Ziegler type polymerization. Steady state     

Maria Merces Marques  C. Costa  F. Lemos  F. Ram?a Ribeiro  A. R. Dias 《Reaction Kinetics and Catalysis Letters》1997,62(1):9-15

In this paper we present a kinetic approach to the analysis of steady-state homogeneous Ziegler-Natta polymerization activity data. The influence of the number of monomeric species that are coordinated to the active site on the apparent rate law is discussed and the equations are fitted to the experimental results.     

864.

Identification of soy protein in meat by pyrolysis-high-resolution gas chromatography     

S K Raghavan  C T Ho  H Daun 《Journal of chromatography. A》1986,351(2):195-202

Pyrolysis-gas chromatography was applied to the characterization of ground beef and soy protein isolate and its mixtures at the 50, 30 and 10% levels. A cryogenic trap pyrolysis mode was employed and the volatile pyrolysates were analysed by a high-resolution capillary gas chromatograph. Two phenolic derivatives, o-methoxy- and dimethoxyphenol, as well as 2,3-dithiabutane are uniquely observed at a large concentration in the soy pyrolysate. Quantification of these characteristic compounds allow the estimation of the level of soy inclusion in the mixture. This approach effectively denotes soy addition up to the 10% level in comminuted beef.     

865.

Molecular structures of two unexpected metal complexes obtained from additions of coordinated phosphines to acetylenes     

P.M. Treichel  W.K. Wong  J.C. Calabrese 《Journal of organometallic chemistry》1978,159(4):C20-C24

The syntheses and structures of two new compounds are reported. The first compound, [Cr(CO)₄]₂[C₄F₂(PPh₂)₄], obtained from Cr(CO)₄(PPh₂H)₂ and CF₃CCF₃ in the presence of one equivalent of BuLi has a structure with the ligand 1,2,3,4-tetrakis(diphenylphosphino)-1,4-difluorobutadiene chelating to two Cr(CO)₄ groups via the 1,4 and 2,3 phosphine groups. A mechanism for the formation of this compound is suggested which involves sequential deprotonation of a phosphine, nucleophilic attack on the fluorocarbon, and fluoride ion elimination. The second compound, CrC₃₆H₂₈P₂O₇, arises from a similar base promoted reaction of Cr(CO)₄-(PPhH₂)₂ and PhCCCOOEt. Here the expected initial product from cyclization of these reactants acts as a nucleophile to attack a second equivalent of the acetylene. The intermediate carbanion from this reaction can undergo a ring closure by displacement of OEt^-, giving the observed product.     

866.

Studies on indian medicinal plants-XLIV: Solanoforthine,a new steroidal alkaloid from solanum seaforthianum. a note on the mass spectrum of solanocapsine     

Esahak Ali  Ajit K. Chakravarty  Satyesh C. Pakrashi  Klaus Biemann  Charles E. Hignite 《Tetrahedron》1977,33(11):1371-1377

The structure of solanoforthine, m.p. 208–10°, [α]_D- 26.6°, a new steroidal alkaloid isolated from Solanum seaforthianum Andr., has been established as 3β-amino-22,26-epimino-16α,23-epoxy-22αH,25βH-cholest- 5- en -23β - ol 3, based on chemical and spectroscopic evidence and by its reduction to solanocapsine 2, another steroidal alkaloid encountered in the same species. The mass spectra of2 and 3 are discussed.     

867.

Tetragonal paramagnetic complex in Gd³⁺ doped Nd₂(SO₄)₃·(NH₄)₂SO₄·8H₂O au]V.M. Malhotra     

H.D. Bist  G.C. Upreti 《Chemical physics letters》1974,28(3):390-392

EPR studies of Gd³⁺ doped in single crystals of Nd₂(SO₄)₃·(NH₄)₂SO₄·8H₂O (hereafter referred to as NASO) at room (RT) and liquid nitrogen (LNT) temperatures exhibit that (1) the metal aquo complex has a tetragonal symmetry with abnormally low magnitudes of crystalline field parameters at RT and (2) NASO undergoes a possible phase transition between RT and LNT.     

868.

Miscibility of small colloidal spheres with large polymers in good solvent     

Hennequin Y  Evens M  Quezada Angulo CM  van Duijneveldt JS 《The Journal of chemical physics》2005,123(5):054906

Nearly athermal colloid-polymer mixtures were studied in the "protein limit." A fluid-fluid transition was observed in mixtures of stearyl-alcohol-coated silica particles and large polystyrene coils in toluene. The ratios of the polymer radius of gyration to the particle radii were q=4.1 and q=5.2. The binodal curves and the critical points were determined. Turbidity measurements and analysis for one set of particles allowed the systems to be mapped onto hard sphere-polymer mixtures. A comparison with recent predictions for the miscibility of model mixtures shows that the experimental binodals lie between the two extreme results for ideal and interacting polymers. The critical colloid volume fraction is also found to decrease with increasing size ratios.     

869.

Nucleophilic substitution at silicon: influence of the attacking allyllithium and aryloxide anion on the stereochemistry and a simple mechanistic proposal     

R.J.P. Corriu  C. Guerin 《Journal of organometallic chemistry》1982,225(1):141-150

     

870.

Detection of primary and secondary amines in energy-related materials using an element-selective glow-discharge detector     

B.A. Tomkins  C. Feldman 《Analytica chimica acta》1980,119(2):283-290

Mutagenic primary polycyclic aromatic amines present in shale oil and synthetic crudes may be readily detected by a simple derivatization and Chromatographic procedure. Nitrogenous bases and amines are extracted from the sample with dilute mineral acid and derivatized with trifluoroacetic anhydride. The derivatized amines are separated by gas chromatography and specifically detected using a glow-discharge detector tuned to an emission wavelength of fluorine. Under these conditions, the aromatic nitrogenous bases, such as acridine, are not detected even though they are present in the sample. As little as 14 ng of fluorine, arising from the derivative of 33 ng of 2,4,6-trimethylaniline, can be detected. The selectivity of the glow-discharge detector for derivatized amines vs. nonderivatized aromatic nitrogenous bases was estimated to be a minimum of 200:1.     

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	$\text{ΔH}{}_{\mathrm{f}}{}^{\mathrm{o}}\text{(c, 298.15 K)/kJ mol}{}^{\mathrm{?1}}$	$\text{ΔH}{}_{\mathrm{s}}\text{/kJ mol}{}^{\mathrm{?1}}$
o-t-butylbenzoic acid	476.2 ± 1.9	99.8 ± 0.4	(at 314.6 K)
m-t-butylbenzoic acid	504.3 ± 1.6	103.0 ± 0.5	(at 326.5 K)
p-t-butylbenzoic acid	502.9 ± 1.7	103.8 ± 0.4	(at 334.1 K)

Massenspektren neuer Phloroglucide,insbesondere solcher mit Valerylseitenketten

Mass spectra of phloroglucinol derivatives recently isolated from African Dryopteris species are presented. Phloroglucides with n-valeryl side chain were found in these ferns for the first time. In the mass spectra they show strong peaks corresponding to loss of propene (C₃H₆) produced by McLafferty rearrangement, as shown in model compounds. Aside of the rottleron change (discussed formerly) this must be considered in order to avoid wrong interpretation, particularly when mass spectra are used to analyse mixtures of homologues, as usually present in the plants. If valeryl side chains are present other methods must be used therefore to measure the amount or show the absence of lower homologues with acetyl side chains.     

A kinetic approach to homogeneous Ziegler type polymerization. Steady state

In this paper we present a kinetic approach to the analysis of steady-state homogeneous Ziegler-Natta polymerization activity data. The influence of the number of monomeric species that are coordinated to the active site on the apparent rate law is discussed and the equations are fitted to the experimental results.     

Identification of soy protein in meat by pyrolysis-high-resolution gas chromatography

Pyrolysis-gas chromatography was applied to the characterization of ground beef and soy protein isolate and its mixtures at the 50, 30 and 10% levels. A cryogenic trap pyrolysis mode was employed and the volatile pyrolysates were analysed by a high-resolution capillary gas chromatograph. Two phenolic derivatives, o-methoxy- and dimethoxyphenol, as well as 2,3-dithiabutane are uniquely observed at a large concentration in the soy pyrolysate. Quantification of these characteristic compounds allow the estimation of the level of soy inclusion in the mixture. This approach effectively denotes soy addition up to the 10% level in comminuted beef.     

Molecular structures of two unexpected metal complexes obtained from additions of coordinated phosphines to acetylenes

The syntheses and structures of two new compounds are reported. The first compound, [Cr(CO)₄]₂[C₄F₂(PPh₂)₄], obtained from Cr(CO)₄(PPh₂H)₂ and CF₃CCF₃ in the presence of one equivalent of BuLi has a structure with the ligand 1,2,3,4-tetrakis(diphenylphosphino)-1,4-difluorobutadiene chelating to two Cr(CO)₄ groups via the 1,4 and 2,3 phosphine groups. A mechanism for the formation of this compound is suggested which involves sequential deprotonation of a phosphine, nucleophilic attack on the fluorocarbon, and fluoride ion elimination. The second compound, CrC₃₆H₂₈P₂O₇, arises from a similar base promoted reaction of Cr(CO)₄-(PPhH₂)₂ and PhCCCOOEt. Here the expected initial product from cyclization of these reactants acts as a nucleophile to attack a second equivalent of the acetylene. The intermediate carbanion from this reaction can undergo a ring closure by displacement of OEt^-, giving the observed product.     

Studies on indian medicinal plants-XLIV: Solanoforthine,a new steroidal alkaloid from solanum seaforthianum. a note on the mass spectrum of solanocapsine

The structure of solanoforthine, m.p. 208–10°, [α]_D- 26.6°, a new steroidal alkaloid isolated from Solanum seaforthianum Andr., has been established as 3β-amino-22,26-epimino-16α,23-epoxy-22αH,25βH-cholest- 5- en -23β - ol 3, based on chemical and spectroscopic evidence and by its reduction to solanocapsine 2, another steroidal alkaloid encountered in the same species. The mass spectra of2 and 3 are discussed.     

Tetragonal paramagnetic complex in Gd3+ doped Nd2(SO4)3·(NH4)2SO4·8H2O au]V.M. Malhotra

EPR studies of Gd³⁺ doped in single crystals of Nd₂(SO₄)₃·(NH₄)₂SO₄·8H₂O (hereafter referred to as NASO) at room (RT) and liquid nitrogen (LNT) temperatures exhibit that (1) the metal aquo complex has a tetragonal symmetry with abnormally low magnitudes of crystalline field parameters at RT and (2) NASO undergoes a possible phase transition between RT and LNT.     

Miscibility of small colloidal spheres with large polymers in good solvent

Nearly athermal colloid-polymer mixtures were studied in the "protein limit." A fluid-fluid transition was observed in mixtures of stearyl-alcohol-coated silica particles and large polystyrene coils in toluene. The ratios of the polymer radius of gyration to the particle radii were q=4.1 and q=5.2. The binodal curves and the critical points were determined. Turbidity measurements and analysis for one set of particles allowed the systems to be mapped onto hard sphere-polymer mixtures. A comparison with recent predictions for the miscibility of model mixtures shows that the experimental binodals lie between the two extreme results for ideal and interacting polymers. The critical colloid volume fraction is also found to decrease with increasing size ratios.     

Detection of primary and secondary amines in energy-related materials using an element-selective glow-discharge detector

Mutagenic primary polycyclic aromatic amines present in shale oil and synthetic crudes may be readily detected by a simple derivatization and Chromatographic procedure. Nitrogenous bases and amines are extracted from the sample with dilute mineral acid and derivatized with trifluoroacetic anhydride. The derivatized amines are separated by gas chromatography and specifically detected using a glow-discharge detector tuned to an emission wavelength of fluorine. Under these conditions, the aromatic nitrogenous bases, such as acridine, are not detected even though they are present in the sample. As little as 14 ng of fluorine, arising from the derivative of 33 ng of 2,4,6-trimethylaniline, can be detected. The selectivity of the glow-discharge detector for derivatized amines vs. nonderivatized aromatic nitrogenous bases was estimated to be a minimum of 200:1.