摘要:

Diethyl sebacate was the major product obtained by ethanolysis of the ozonization products of ethyl 10-undecenoate in the temperature range 28 to 170 °C. Mixed esters of sebacic acid were similarly obtained, in poor to moderate yields, by alcoholysis of the ozonization product from an alkyl ester of 10-undecenoic acid in the appropriate alcohol. Sebacic acid half esters are prepared by a similar treatment of the ozonization products from 10-undecenoic acid itself. Ester formation has been shown to proceed mainly by rearrangement of an alkoxyhydroperoxide, with oxidative esterification of an aldehyde intermediate contributing to a minor degree.

ISSN:0008-4042    

DOI:10.1139/v65-042

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The mass spectra of lycofawcine (base L fromL.fawcettii) and some of its derivatives are recorded and discussed. On the basis of the interpretation of the mass spectra a structure (IV) is proposed for lycofawcine. Experiments which confirm structure IV are described, and the stereochemistry of lycofawcine is discussed.

ISSN:0008-4042    

DOI:10.1139/v65-043

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The low-melting form of β-aminocrotononitrile is a mixture of two components, one of which is the high-melting isomer. Isomerization reactions between the high- and low-melting forms occur very easily, reactions in solution being subject to acid–base catalysis. Self-condensation of β-aminocrotononitrile gives 4-amino-1,3-dicyano-2-methylpenta-1,3-diene which readily cyclizes to 2-amino-5-cyano-4,6-lutidine.

ISSN:0008-4042    

DOI:10.1139/v65-044

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

A series of halogenated phthalides was prepared in which there was a systematic variation in the identity, position, and degree of activation of the halogen, and in the activation of the methylene group. A study was made of the selective reductive removal of halogen in the presence of another halogen, or of a nitro group.

ISSN:0008-4042    

DOI:10.1139/v65-045

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

A study was made to determine the relative reactivity of the toluene–benzene pair in a nitronium salt nitration, using the method of competitive rate determination. Despite difficulties encountered in ensuring homogeneous reaction conditions owing to the high speed of reaction the relative rates (toluene/benzene) obtained under certain conditions attained a range (25–30) which is considered to represent the range of relative reactivity and it corresponds to the known reactivity of toluene-benzene in nitric acid nitration. On the basis of these results there seems to be no reason to suppose that nitronium salt nitration involves a mechanism different from that of the nitric acid nitration.

ISSN:0008-4042    

DOI:10.1139/v65-046

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The thermal and photochemical decomposition of methyl benzoate (p-tolylsulfonyl)hydrazone salts in 1,2-dimethoxyethane, 1,2-diethoxyethane, or diglyme gives rise to benzaldehyde dimethyl acetal, methyl benzoate azine (II),meso-1,2-diphenyl-1,2-dimethoxyethane, and methyl α-(p-tolylsulfonyl)benzyl ether. The thermal decomposition in the presence of diethyl fumarate produced diethyl 3-methoxy-3-phenyl-trans-1,2-cyclopropanedicarboxylate (XIV) in 62% yield; a low yield (4%) of the two isomeric forms of 1-methoxy-2-n-octyl-1-phenyl-cyclopropane (V) was formed in 1-decene. The thermal and photochemical decomposition of potassium 4-pentenyl benzoate (p-tolylsulfonyl)hydrazone (XVIII) produced 1-phenyl-2-oxabicyclo[4.1.0]heptane (XXI) in 14 and 21% yield respectively. These products provide additional evidence for the occurrence of alkoxydiazoalkanes and suggest alkoxycarbenes as possible intermediates in the decomposition of ester (p-tolylsulfonyl)hydrazone salts.

ISSN:0008-4042    

DOI:10.1139/v65-047

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The decay of the blue emission from the active nitrogen – iodine flame has been measured at iodine pressures down to 1.4 × 10−4torr. Extrapolation of the decay rate to zero iodine pressure yields a value of 0.89 ± 0.41 s−1for the first-order rate constant in absence of iodine, corresponding to a mean lifetime of 1.1 s for thestate of N2. The rate constants for the reactionsandare (2.6 ± 0.3) × 10−11exp (−68 ± 34/RT) and (8.3 ± 1.2) × 10−14 cm3molecule−1s−1respectively.

ISSN:0008-4042    

DOI:10.1139/v65-048

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The proton resonance spectra of a number of Lewis acid –N,N-dimethylformamide adducts in 2-nitropropane and methylene chloride solutions have been investigated and an attempt has been made to correlate the relative strength of Lewis acids with the chemical shift of the methyl protons. The order obtained for the relative strength of Lewis acids shows good agreement with the results obtained by other methods. The complex formation has taken place on the carbonyl oxygen of theN,N-dimethylformamide in all cases. The DMF – Lewis acid mole ratios were 1:1 in ZnCl2, AlCl3, PF5, BiCl3, InCl3, AsF5, SbCl5, SbF5, BF3, BCl3, BBr3. The 2:1 DMF – Lewis acid complexes of ZnCl2, SnCl4, SnBr4, Snl4, TiCl4, ZrBr4have also been investigated.

ISSN:0008-4042    

DOI:10.1139/v65-049

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

TheGvalues of the major products of the γ-radiolysis of liquid ethanol at a dose of 2 × 1020 eV/g are: hydrogen, 4.2; acetaldehyde, 1.9; 2,3-butanedio1, 2.2;G(—C2H5OH) = 7.5. At progressively lower dosesG(H2) increases to a maximum of 5.0. The yield of water,G(H2O) = 0.5, is equal to the sum of the yields of the C2fragments found in the other products.The approximate yields of three kinetically distinguishable sources of hydrogen were found to beG(H2) = 2.7 andG(unscavengeable H2) = 1.5. The half-life of solvated electrons with respect to reactions such asis 3 μs.Both 1,3-pentadiene and benzene inhibit hydrogen and glycol formation but neither affect the high dose yield of acetaldehyde. Pentadiene reacts with H atoms and other radicals and possibly also withBenzene appears to inhibit hydrogen and glycol formation mainly by an unidentified activation transfer process.

ISSN:0008-4042    

DOI:10.1139/v65-050

出版商:NRC Research Press    

年代:1965

数据来源: NRC

摘要:

The chromatography of piperidine, cyclohexylamine, benzylamine, and morpholine hydrochlorides on unwashed Whatman No. 1 and No. 17 papers int-butanol: acetic acid: water (2:1:1) leads in each case to partial conversion to the acetate salt, the mobility of which differs from that of the hydrochloride. The interconversion is reduced but is not prevented by the use of acid-washed papers and is increased again when the acid-washed papers are treated with sodium, potassium, calcium, or magnesium acetate prior to chromatography. The salt interconversion is continuous during development of the chromatograms, extended development leading to complete disappearance of the hydrochloride. Quantitative chromatography of piperidine and morpholine hydrochlorides revealed that the extent of salt interconversion is ca. 12% on unwashed and calcium ion washed Whatman No. 17 papers, ca. 6% on sodium ion washed papers, and ca. 1% on acid-washed papers. Piperidinium ions become bound to unwashed, acid-washed, and salt-washed Whatman No. 17 papers during chromatography in aqueous solution just as they do to the hydrogen, sodium, and calcium forms of the carboxylate ion exchanger Amberlite IRC-50 under similar conditions, indicating that a cation exchange mechanism involving carboxyl groups in the paper is responsible for the observed salt interconversion.

ISSN:0008-4042    

DOI:10.1139/v65-051

出版商:NRC Research Press    

年代:1965

数据来源: NRC