摘要:

The reactions of a series of phosphylating agents (RR′P(O)X) with ethanolamine have been examined, and relative yields of the products from the nucleophilic amino and hydroxyl moieties determined. In general the amount ofO-phosphylation increased as R and R′ were changed from dimethylamino through alkoxy to methyl and as the leaving group (X) was changed from OP(O)RR′ to CN. The only exceptions occurred when R was dimethylamino and X was Cl. When X was F, onlyO-phosphylation was observed. Thus, a wide range of essentially continuously varying selectivities was found.The results are discussed in terms of the amount of charge transfer involved in the formation of the transition state which is assumed to be determined by the electrophile. When the charge transfer is small, the contributions to the activation energy of such factors as solvation and ionization potential of the nucleophile are most important, resulting inN-phosphylation. As the amount of charge transfer increases, the energy of bond formation becomes the dominant factor andO-phosphylation is preferred.

ISSN:0008-4042    

DOI:10.1139/v70-223

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

In pyridine or 2-methyl-2-propanol solution, the kinetics of the reaction of sarin with methanol in the presence of amines to produce the ester, methyl isopropyl methylphosphonate, is shown to be of first order with respect to each of the three components. By varying the amine it was deduced that the amine acts as a general base catalyst but the catalysis is subject to large steric effects.

ISSN:0008-4042    

DOI:10.1139/v70-224

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The mass spectra of the hexafluoroacetylacetonates (hfacac) and trifluoroacetylacetonates (tfacac) of Al(III), Cr(III), Fe(III), Fe(II), Cu(II), and Zn(II) are reported. The main features of the spectra are discussed. Compared with the spectra of the acetylacetonates (acac), substitution of CF3for CH3in these complexes leads to more extensive fragmentation of the molecular ions. For example, ions corresponding to loss of •CF3radicals are more abundant than those corresponding to loss of •CH3radicals. The appearance potentials (a.p.'s) of the molecular ions and, where possible, of fragment ions formed from the molecular ion by loss of •CF3, •CH3, or ligand radicals are reported. The a.p.'s of the molecular ions are more sensitive to the nature of the ligand than to the metal. Thus, for the metal chelates studied here the a.p.'s of the molecular ions from ML2and ML3(L stands for ligand) were 9.95 ± 0.25 V for L = hfacac, 9.05 ± 0.35 V for L = tfacac, and 8.3 ± 0.35 V for L = acac. The energy required to dissociate a •CF3or •CH3radical from the molecular ion is sensitive to the nature and valency of the metal M, being low (relatively) for Al(III) and Fe(III), and high (relatively) for Cr(III) (inferred) and Fe(II). This variation is discussed in terms of the effect of substituent, and of interaction of metal d orbitals with the ligands.

ISSN:0008-4042    

DOI:10.1139/v70-225

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

3-Arylisoxazol-5-ones and 5-arylisoxazol-3-ones were prepared and converted to theN-methyl andO-methyl derivatives by reaction with diazomethane. The halogen in 3-phenyl-5-chloroisoxazole was replaced by several alkoxy and thioalkoxy groups. The 3,5-disubstituted isoxazoles thus obtained reacted withn-butyllithium to form the 4-lithio derivatives, as shown by conversion to 4-carboxylic acids and 4-iodocompounds. 3-Methoxy-5-phenylisothiazole was also lithiated at the 4-position.

ISSN:0008-4042    

DOI:10.1139/v70-226

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The syntheses ofcis- andtrans-2-aminocyclohexanols and ofcis- andtrans-2-ethylaminocyclohexanols are described. Thecisisomers were prepared by treatment of the correspondingtrans-2-acetamidocyclohexanols with thionyl chloride followed by hydrolysis of the resulting intermediate oxazolines. The 2-aminocyclohexanols were converted to 2′-(cis- andtrans-2″-hydroxycyclohexyl)aminoethyl 1-phenyl-cyclopentanecarboxylate hydrochlorides (1and2, R = H) by treatment with 2′-bromoethyl 1-phenyl-cyclopentanecarboxylate, but attempts to convert the 2-ethylaminocyclohexanols to1and2(R = C2H5) by a similar reaction were unsuccessful. The anticholinesterase activities of several of the compounds are discussed, as are the potencies of1and2(R = H) in protecting mice and rats from sarin poisoning.

ISSN:0008-4042    

DOI:10.1139/v70-227

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The syntheses of simple substituted glucoses (i.e., 2-O-, 3-O-, and 6-O-[(N-methyl-N-2-hydroxyethylamino)ethyl]-D-glucopyranoses) and simple crosslinked glucoses (i.e.,N-methylaminobis[O-(N-2-ethyl)-D-glucopyranoses]) with glucose linkages at 2,2′-O-, 3,3′-O-, 6,6′-O-, 2,6′-O-, and 3,6′-O-positions are described. These result from the reactions of "blocked" glucoses withN-methylbis(2-chloroethyl)amine. The new derivatives were characterized by gas–liquid chromatography and electrophoresis. Cotton cellulose modified withN-methylbis(2-chloroethyl)amine to incorporate 0.034 mole of reagent perD-glucopyranosyl unit was hydrolyzed to glucose and substituted glucoses; the substituted glucoses were identified by chromatographic and electrophoretic comparisons with the foregoing authentic glucose derivatives. The relative distribution of (N-methyl-Nhydroxyethylamino)ethyl groups among the 2-O-, 3-O-, and 6-O-positions was 2.30:0.28:1.00. The distribution of crosslinkages among the 2,2′-O-, 2,6′-O-, and 6,6′-O-positions was 2.10:3.72:1.00; these are the only crosslinked derivatives found. The monofunctionally substituted fraction (having a single reagent unit in the substituent group) accounted for 42.6% of the nitrogen; the crosslinked fraction (having a single reagent unit in the crosslink) accounted for 25.8%; complex products accounted for the remainder of the nitrogen of the crosslinked cotton.

ISSN:0008-4042    

DOI:10.1139/v70-228

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

The relative importance of addition and reduction, as well as thesyn:antiselectivity of those processes, were determined for the reactions of five Grignard reagents with norbornen-7-one. Reduction is important or dominant in the reactions of Grignard reagents having β-hydrogen and there is a strong preference for the hydride transfer to occur from thesynface of the carbonyl group. Addition shows the analogous stereochemical preference with higher selectivity than reduction.

ISSN:0008-4042    

DOI:10.1139/v70-229

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

When 2-aminophenylsulfonylacetic acid (3) was heated under reflux in an excess of dilute sodium hydroxide solution, the only product identified was 2-methylsulfonylaniline (6). When 2-nitrophenyl-sulfonylacetic acid was treated under the same conditions, the major products identified were 2-methyl-sulfonylnitrobenzene (7), 2-nitrophenol (8), and orthanilic acid (13); minor products of this reaction were6and 3-methylsulfonyl-3′-nitro-4-amino-4′-hydroxybiphenyl (12). The same products were obtained although the yields were different when7was boiled with alkali, but the reaction of 4-methylsulfonyl-nitrobenzene (15) with alkali was less complex and 4-nitrophenol (16) was the only major product. The biphenyl12was also formed in small yield whenN-(2-methylsulfonylphenyl)hydroxylamine (19) was treated with alkali and its formation in these reactions was investigated in detail. It was concluded that12arises from7and19, but it could also be prepared from19and 2-chloro- or better, 2-fluoronitrobenzene, in alkaline solution, and based on all these observations, a mechanism for its formation is suggested. The genesis of the various other products is also discussed. Reference is made to the infrared spectra of sulfones.

ISSN:0008-4042    

DOI:10.1139/v70-230

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

WhenN-(2-methylsulfonylphenyl)hydroxylamine (4) was treated with dilute sodium hydroxide solution the major product was always 2,2′-di(methylsulfonyl)azoxybenzene (5). At room temperature other significant products were 2-hydroxy-2′-methylsulfonylazoxybenzene (6a) and 2-methylsulfonylnitrobenzene (2), while6awas also formed at reflux together with small amounts of 2-hydroxy-2′-methylsulfonylazobenzene (8), 2-methylsulfonylaniline (7), 3-methylsulfonyl-3′-nitro-4-amino-4′-hydroxybiphenyl (3), and2. The compounds5,6a, and7were also obtained when 2-methylsulfonylnitrosobenzene (9) was boiled with alkali. The decomposition ofN-(4-methylsulfonylphenyl)hydroxylamine (16) in dilute alkali at room temperature gave a quantitative yield of 4,4′-di(methylsulfonyl)azoxybenzene (17) and at reflux, mixtures of17and 4,4′-di(methylsulfonyl)azobenzene (18) were obtained. The modes of formation of the various products from the two hydroxylamines are discussed.

ISSN:0008-4042    

DOI:10.1139/v70-231

出版商:NRC Research Press    

年代:1970

数据来源: NRC

摘要:

In acetonitrile, iron(II) forms stable 1:1 complexes with chloride, bromide, and iodide and both 1:1 and 1:2 complexes with thiocyanate. Stepwise formation constants for the complexes were determined spectrophotometrically by a mole-ratio method. The logKvalues are: FeCl+, 5.8; FeBr+, 5.5; FeI+,4.3; Fe(SCN)+, 5.5; and Fe(SCN)2, 3.7.

ISSN:0008-4042    

DOI:10.1139/v70-232

出版商:NRC Research Press    

年代:1970

数据来源: NRC