摘要:

The syntheses of 39 novelp-phenylenediamine derivatives are reported, including a number in which one of the nitrogens in thep-phenylenediamine is part of a heterocyclic ring. These compounds were prepared as part of a program seeking effective antiozone agents having little or no dermatitic toxicity.

ISSN:0008-4042    

DOI:10.1139/v67-039

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Ultraviolet irradiation of benzene solutions of 4′-dimethylamino-2,2,2-tris-(p-dimethyl-aminophenyl)-acetophenone (I) and 2,2-bis-(p-dimethylaminophenyl)-2-phenylacetophenone (II) and iodine gave crystal violet triiodide and malachite green triiodide, respectively. Irradiation of I in hexane and in the presence of air gave a brilliant blue solid III. Analytical and spectral data support a proposed structure which is a tetraoxide, or its ion-pair equivalent, of the homolytic cleavage products of I.

ISSN:0008-4042    

DOI:10.1139/v67-040

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The relative ease of hydrogenolysis of ether solutions of acetals or ketals is much greater with AlH2Cl than with AlH3. Conversion of the speciesone into the other is fast, and is accomplished by the addition of the appropriate quantity of AlCl3or LiAlH4to solutions of AlH3or AlHCl2, respectively. Gradual addition of an equimolar proportion of AlCl3in ether to an ether solution of equimolar proportions of LiAlH4and acetal or ketal first forms AlH3, which is rapidly converted into AlH2Cl as more AlCl3is added. During the time of this addition (≤ 10 min) little reduction by AlH3takes place. Most of the reduction is done by the species AlH2Cl when the AlCl3is completely added.

ISSN:0008-4042    

DOI:10.1139/v67-041

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The temperature dependence of the formyl proton shieldings of 9-anthraldehyde and 9-phenanthraldehyde in chloroform solutions has been measured. Four concentrations in the range 0.5–5.0 mole % were examined over the temperature interval − 60 to + 90 °C. From these results, the enthalpies and entropies of formation have been estimated for the complex formed by the self-association of two aldehyde molecules. The calculations indicate the ΔHand ΔSvalues to be − 1.9 ± 0.3 kcal/mole and − 6 ± 1 e.u., respectively. These results are compared with other available data.

ISSN:0008-4042    

DOI:10.1139/v67-042

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The ozonolysis of indene in ethanol yields 3-hydroxy-4,5-benzo-7-ethoxy-l,2-dioxacyclo-heptane and 3-ethoxy-4,5-benzo-7-hydroxy-1,2-dioxacycloheptane, roughly in a 1:1 ratio, thus showing that the cleavage of the primary indene ozonide follows the two possible courses: via the zwitterionsand, respectively.

ISSN:0008-4042    

DOI:10.1139/v67-043

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The 15.1 Mc/s13C nuclear magnetic resonance spectra of 15 aliphatic and alicyclic ketones having a three-membered ring alpha to the carbonyl group have been obtained and the shieldings of their carbonyl carbon nuclei are reported. A number of derivatives of bicyclo-[4.1.0]heptan-2-one, bicyclo[3.1.0]hexan-2-one, spiro[2.5]octan-4-one, and spiro[2.4]heptan-4-one have been included. The primary objective was to investigate the question of conjugation of the cyclopropyl ring with a carbonyl grouping, since we had shown previously that13C shieldings of carbonyl carbons are significantly affected by conjugative interactions. The13C data for several related compounds were obtained to aid in our assessment of the cyclopropyl results. Some evidence of cyclopropyl conjugation is presented.

ISSN:0008-4042    

DOI:10.1139/v67-044

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The13C spectra of the methyl esters of 20 substituted benzoic acids have been recorded, and the chemical shifts of the carbon nuclei of the carbomethoxyl group and aromatic ring have been measured. These shielding results are discussed and compared with the corresponding data for similar series of acetophenones and anisoles. Some evidence of steric inhibition of conjugation is presented for certain diortho-substituted examples.

ISSN:0008-4042    

DOI:10.1139/v67-045

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The rates of rearrangement of a wide variety of α-silylcarbinols have been measured. Hammett plots of logkvs. σ have been made for several systems, and values for ρ, for the energy of activation, and for the entropy of activation have been obtained. A mechanism which is consistent with the above data, and which involves a cyclic three-membered transition state, has been proposed for the α-silylcarbinol to silyl ether rearrangement.

ISSN:0008-4042    

DOI:10.1139/v67-046

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Mono-O-(methylsulfonylethyl)-d-glucoses needed for comparison with the cleavage products obtained by acid hydrolysis of methyl vinyl sulfone modified cotton celluloses have been prepared. Several new glucose derivatives were prepared as intermediates in the synthesis of the desired2-O-, 3-O-, and 6-O-(methylsulfonylethyl)-d-glucoses. The reactions were monitored by gas–liquid chromatography; use was made of trimethylsilyl derivatives as necessary. The substituted glucoses were obtained as glassy solids.

ISSN:0008-4042    

DOI:10.1139/v67-047

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

O-(2-Diethylaminoethyl)cellulose (degree of substitution 0.048) was prepared by reacting cotton cellulose, in the form of fabric, with 2-diethylaminoethyl chloride in the presence of excess sodium hydroxide at room temperature. The modified cellulose was hydrolyzed and the substituted glucoses were identified by chromatographic comparison with authentic 2-O-, 3-O-, and 6-O-(2-diethylaminoethyl)-d-glucoses in the form of their trimethylsilyl ethers. Syntheses of authentic 2-O-, 3-O-, and 6-O-(2-diethylaminoethyl)-d-glucoses are described. The relative distribution of 2-diethylaminoethyl groups among the 2-O-, 3-O-, and 6-O-positions of thed-glucopyranosyl residue of cotton cellulose was found to be 1.27:0.35:1.00.

ISSN:0008-4042    

DOI:10.1139/v67-048

出版商:NRC Research Press    

年代:1967

数据来源: NRC