On treatment with ammonia, 10-bromocamphor gave d-α-campholenic amide which, on treatment with hydrochloric acid, stereochemically isomerized to the levorotatory amide. As a means of studying the principle that underlies this transformation, isomerization was attempted on original α-campholenic acid with mineral acid. It was clarified from infrared absorption spectra that the double bond in the case of alkali-formed products, is situated in a methylene group outside the cyclopentane ring and, in the case of acid-treated products, inside the ring. The former was termed α-campholenic acid-I and the latter α-campholenic acid-II. The properties of α-campholenyl alcohol-I and -II, formed by the respective reduction of the esters of acid-I and -II, were determined.

抄録全体を表示

The positions of the double bonds in α-campholenic acid-I and -II were determined by investigating their respective oxidation products, confirming thereby the results obtained by the spectrum method. An attempt was also made to clarify the process of conversion from 10-bromocamphor into α-campholenic acid, proving it to be a straight reaction without passing through any intermediates such as α-camphenone.

抄録全体を表示

(1) It has been demonstrated that dibromination of 7-oxocholestanyl acetate or benzoate gives corresponding 6, 6-gem-dibromide. (2) The structure of these dibromides was determined by characteristics absorptions in the ultraviolet and infrared spectra and from the results of some chemical reactions. (3) Dibromination of methy 13α, 12α-diacetoxy-7-oxocholanate was also examined.

抄録全体を表示

3-Hydroxy-N-methyl-c-normorphinan, synthesized earlier, was submitted to the Hofmann degradation and by the synthesis of its degradation products, its structure was confirmed.

抄録全体を表示

The usefulness and applicability of the small intenstines of mice for the assay of acetylcholine and atropine were examined and the results were treated statistically.

抄録全体を表示

1) A concentration-action relationship of acetylcholine was demonstrated using isolated intestines of 20 mice. 2) For mean responses of six acetylcholine concentrations was fitted a logistic sigmoid curve by the method of maximum likelihood. 3) The maximum likelihood estimate of the mean slope was 1.146, which was proved not to be significantly different from the theoretical value of one.

抄録全体を表示

1) Rr values of several photographic developing agents were determined (Table I). 2) When sample is applied around the center of the filter paper, Rr value is estimated by the following equation : [numerical formula] where Rr represents Rf value of the case in which the sample is applied at the center of the paper, c is the distance of initial spot from the center of the paper, b is the distance of the solvent front from the initial spot, and a is the distance moved by the sample from the initial spot.

抄録全体を表示

Infrared absorption spectra of pyridine 1-oxide and 15 kinds of its alkyl derivatives were measured and characteristic absorption band for the N-oxide group was established. The effect of ring substituents on the N-O frequency and the effect of the introduction of N-O function on ring vibration were discussed in comparison with the spectra of corresponding pyridine bases. The absorption of strong intensity always appearing in the region between 1200 and 1300 cm^-1 in these compounds were assigned to that based on the N-O stretching mode. This absorption was always displaced to lower frequencies in the presence of methanol, thereby proving its solvation effect. The frequencies of this absorption showed sensitive relationship to the position of the alkyl group in the ring, the effect being especially marked in 3-alkyl group which caused a shift to the higher frequency. A reasonable relation was found to exist between N-O frequency and electronical nature of the substituents in several of the 4-substituted pyridine 1-oxides. There was no marked relationship between the out-of-plane bending frequencies of ring hydrogen in 1-oxides and those in corresponding pyridines. The behavior of the ring double-bond vibration in 1-oxide compounds was contrasting to that of the corresponding pyridines.

抄録全体を表示

Methyl oleanolate 2-monoglucuronoside was prepared from methyl oleanolate and α-BGM in the presence of mercuric cyanide as a catalyst. Oleanolic acid 2, 28-diglucuronoside was obtained from oleanolic acid 28-methyltriacetylglucuronoside with mercuric cyanide and α-BGM. This substance had a saponin-like properties and the hemolytic activity of diglucuronoside was compared with that of other saponins.

抄録全体を表示

The treatment of dl-threo-1-phenyl-1-benzoyloxy-2-amino-3-bromopropane (I) hydrobromide in basic media yielded dl-1-phenyl-2-benzoylaminoprop-1-en-3-ol (or dl-1-phenyl-2-benzoyliminopropan-3-ol) (IV) via dl-threo-2-phenyl-4-phenylhydroxymethyl-⊿²-oxazoline (II). dl-threo-1-Phenyl-2-benzoylaminopropane-1, 3-diol (III) was also formed by treatment of hydrobromide of (I) with potassium acetate and hydrous ethanol. These formation mechanisms were discussed on the ground of stereochemical findings.

抄録全体を表示

1, 2, 3, 6, 7, 12b-Hexahydro-4H-1, 3-dioxolo [j] pyridazo [3, 2-a] isoquinoline (II) was synthesized by cyclizing 2-(3, 4-methylenedioxyphenethyl) hexahydro-3-pyridazinone followed by reduction with sodium borohyride. This is the first exmple of azabenzoquinoline type of compound recorded in literature. Phrmacological property of the compound (II) is now being examined.

抄録全体を表示

Allylpyridylcarbinols (α or γ) were obtained from allyl picolyl ethers (α or γ) by the application of sodium amide in benzene. When the same reactions was carried out in xylene at 130∼140°, the yield of rearrangement product increased in the γ-compound, while a non-viscous oil was obtained from the α-compound. This non-viscous oily product was found to be identical with propyl α-pyridyl ketone.

抄録全体を表示

7-Hydroxy-π-apocamphane (IX) and 7-hydroxy-10-apocamphor (XIII) were prepared from l-π-apocamphane-7-carboxylic acid (IV) and α-ketopinic acid (X) by the Hofmann or Curtius reaction and followed by deamination of the corresponding amines. Both compounds were found to be quite stable in constrast to 7-hydroxy-π-apocamphor (II). 7-Hydroxy-π-apocamphane (IX) was obtained in an optically inactive form, whereas 7-hydroxy-10-apocamphor (XIII) in an active form without steric inversion. The reaction mechanism was discussed.

抄録全体を表示

A quaternary base magnoflorine was isolated from the root of Thalictrum Thunbergii DC. of the Ranunculaceae family.

抄録全体を表示

Ureido [¹⁴C] succinic acid and orotic [2-¹⁴C] acid, which are metabolic intermediates for nucleic acid pyrimidines, were synthesized by an improved method of Nyc and Mitchell starting with aspartic acid and urea [¹⁴C], which is more easily available than potassium cyanate [¹⁴C]. The yield of orotic [2-¹⁴C] acid was 15.7% based on urea [¹⁴C].

抄録全体を表示