Colorless Prisms Research Articles

オロチン酸の製剤学的研究 (第2報)

Water soluble products were isolated as crystals, when orotic acid and equimolar monoamine were reacted in the concentrated water solution. All of 16 sorts of the product obtained were colorless prisms and the analytical values were coincided with the theoretical ones calculated as the binding ratio of orotic acid to amine to be 1:1. When either nicotinamide or ammonia was reacted with orotic acid by the same method, a similar product was obtained in the ratio of 1:1. The products were very soluble in water and the solubilities were varied with the kind of amine and the structure. There is an interrelative correlation between the solubility and the melting point, that is, the product having lower melting point possesses a larger solubility.

SAPONINS OF TIMO (ANEMARRHENAE RHIZOMA). I

1. The fresh rhizomes of Anemarrhena asphodeloides BUNGE collected in July were found to contain sarsasapogenin and markogenin, as previously reported by Takeda, et al., and also one more sapogenin, neogitogenin (m.p. 253-254°, [α]D19-66.4° (c=0.24, CHCl3); diacetate, m.p. 215-219°, [α]D18-112° (c=0.41, CHCl3)).2) A commercial crude drung“Timo” (the dried and stored rhizomes of A. asphodeloides BGE.) contained sarsasapogenin, and six steroid saponins were detected in its methanol extract. They were respectively named timosaponin A-I, A-II, A-III, A-IV, B-I, and B-II. A-III was isolated as colorless prisms, m.p. 317-322° (decomp.), [α]D27-41.6° (c=0.27, dioxane) and B-I as amorphous powder, m.p. 170-180°.3. Timosaponin A-III was composed of sarsasapogenin, D-glucose, and D-galactose, and the sugar moiety was presumed to be a biosc. B-I and A-I were regarded, respectively, as a parent saponin having another mole of glucose, and the prosapogenin, of A-III.

モクレン科植物アルカロイド研究 (第28報)

Alkaloids contained in Michelia compressa MAXIM. var. formosana KANEHIRA (Japanes name “Taiwan-Ogatamanoki”), a plant of the Magnoliaceae family indigenous to Formosa, were examined. From the heartwood of this tree, tertiary non-phenolic beses were isolated as colorless prisms, m.p. 180-181°, and pale yellow needles, m.p. 279-281°(decomp.). The main alkaloid of m.p. 180-181° was named “ushinsunine.” This base corresponds to the molcular formula of C18H17O3N, [α]D -113.6° (EtOH), it is positive to the Gaebel and Labat's color reaction for methylenedioxy group, and does not contain methoxyl group. It easily forms a basic monoacetate of colorless prisms, m.p. 202-203°, C18H16O2N(OCOCH3). Infrared spectrum of ushinsunine revealed the presence of alcoholic hydroxyl and methylenedioxy groups (Chart 1) and its ultraviolet spectrum suggested the structure of an aporphine-type base (Fig. 1). It was thereby assumed that ushinsunine is an aporphine-type base represented by the experimental formula of C18H17O3N=C16H11(OH)(O2CH2)(NCH3).The other base of m.p. 279-281° (decomp.) was proved to be the identical with oxoushinsunine, m.p. 280-281°(decomp.), obtained by oxidation of ushinsunine with pyridine and chromium trioxide, as will be described in a later report.Water-soluble quaternary bases were obtained in the form of magnoflorine (I) and a minute amount of a new base as a picrate.

ジヒドロ海人酸及びその関連化合物の合成研究 (第7報)

From the yellowish crystalline powder, obtained by the hydrolysis of 1-ethoxy-carbonyl-2-carboxy-3-cyanomethyl-4-isopropylpyrrolidine, dihydrokainic acid, C10H17O4N, was successfully isolated and purified as colorless prisms, m.p. 253° (decomp.). Infrared absorption spectrum and Rf value of this substance were measured.

コクサギ根皮のアルカロイド (第6報)

Although the structure of kokusaginine has been determined by Anet et al., it was also confirmed by the following procedure. Catalytic reduction of kokusaginine with PtO2 in ethanolic solution produced colorless cubic crystals of the formula, C14H17O4N (IV), m.p. 182-183°, which by demethylation with conc. HCl, gave the compound, C13H15O4N (V), m.p. 263-264°. With acetic anhydride and pyridine it yielded a monoacetate, C15H17O5N, m.p. 235-236°, in colorless prisms. (IV) and (V) are assumed to be 3-ethyl-4, 6, 7.-trimethoxycarbostyril and 6, 7.-dimethoxy-3-ethyl-4-hydroxycarbostyril, respectively, as in the case of dictamnine, skimmianine, and kokusagine. On the other hand, the compound (V) was prepared synthetically as follows: Methyl 6-aminoveratrate and butyric anhydride gave methyl 6-(N-butyrylamino) veratrate (X), m.p. 107.5-108.5°, which, when treated with Na in toluene, afforded 6, 7.-dimethoxy-3-ethyl-4-hydroxycarbostyril, m.p. 263-264° (monoacetate, m.p. 235.5-236°). This substance is identical with (V) (as was also the acetate). The structure of kokusaginine, therefore, is 6, 7.-dimethoxydictamnine.

芳香環状異項環の分極 (第104報)

3, 5-Dinitro-4-cyanopyridine was prepared from 3, 5-dinitro-4-chloropyridine by heating it with cuprous cyanide, directly or in nitrobenzene, as platelet crystals of m.p. 140°, with a maximum yield of 45%. Treatment of 4-hydroxy-3, 5-dinitro-α-picoline 1-oxide with phosphorus trichloride in ethyl acetate gave 3, 5-dinitro-4-hydroxy-α-picoline in 87% yield, as pale yellow plates, m.p. 269° (decomp.). Further heating of the latter with phosphoryl chloride gave 3, 5-dinitro-4-chloro-α-picoline in 73% yield as colorless prisms, m.p. 108°. The latter was easily sublimable and its heating with cuprous cyanide failed to yield 4-cyano derivative, resulting in the recovery of 70-90% of the starting material.

ピペリヂルカルビノール類の合成研究 (第1報)

In the hope of finding compounds possessing analgesic properties, six compounds possessing the following general formula were prepared: The compounds were prepared by the oxidation of α-, β-, and γ-phenyl-N-methyl-piperidylcarbinols with a calculated amount of chromic acid in glacial acetic acid to α-, β-, and γ-benzoyl-N-methylpiperidines to which were applied phenyl- or 2-thienylmag-nesium bromide. The compounds synthesized are as follows:R1=R2=phenyl, n=0, n′=4: Colorless prisms, m.p. 88.5-89.5°.R1=R2=phenyl, n=1, n′=3: Colorless needles, m.p. 147-148°.R1=R2=phenyl, n=2, n′=2: Colorless granules, m.p. 134-136°.R1=phenyl, R2=2-thienyl, n=0, n′=4: Colorless needles, m.p. 93-94°.R1=phenyl, R2=2-thienyl, n=1, n′=3: Colorless needles, m.p. 142-143°.R1=phenyl, R2=2-thienyl, n=2, n′=2: Colorless rhombs, m.p. 147-148°.

ヂアゾベンゼンスルフォン酸とシステインとの反應について

The reaction of diazobenzene sulfonic acid with cysteine was investigated as a model reaction of the former with the assumed free SH groups in the amylase (so-called SH-enzyme) molecule. Three reaction products were isglated: (I) yellow colored plates, (II) cystine, and (III), colorless stable prisms (the yield of (III) was higher than that of (II) ). (I) was unstable to heating as it was decomposed to evolve nitrogen gas when heated at 100° in water. Here (II) and (III) could be separated again from the reaction mixture. (III) was richer in yield than (II). Physical and chemical properties indicated that (III) had the structure:_??_(I) must be an intermediate to (II) and (III) and had perhaps the structure:_??_Thus it is supposed that if diazobenzene sulfonic acid acts on the free -SH groups in the amylase molecule, it might couple with -SH rather than oxidizes them. This reaction may play some role in the inhibitive action of diazobenzene sulfonic acid on amylase.

Studies on the Alkaloids of Magnoliaceous Plants. VIII

The authors isolated and identified three kinds of quaternary bases from the bark of Magnolia denudata Desr., belonging to the Magnoliaceae, which grows in Japan. The one was isolated as the chloride, crystallizing in colorless prisms, m.p. 260-261° (decomp.), and the other two as the picrates, crystallizing in yellow needles, m.p. 181.5-182°, and in orange yellow prisms, m.p. 222-223°, respectively. As a result of examination, it has been confirmed that the first two bases are salicif oline chloride (I) and magnocurarine (II) picrate, respectively. The last picrate of m.p. 222-223° is now being studied.

Studies on the Alkaloids of Magnoliaceous Plants. V

From the bark of Magnolia Kobus DC., belonging to the Magnoliaceae, a quaternary base was isolated. This base was obtained as a chloride, crystallized in colorless plates or prisms, m. p. 260-261° (decomp.), and has the composition of C12H20O2NCl. This base was proved to be identical with salicifoline chloride [β-(3-hydroxy-4-methoxyphenyl)-ethyl-trimethylammonium chloride], an alkaloid found in the bark of Magnolia salicifolia Maxim. Furthermore, the remaining alkaloids in the mother liquor obtained after removing this base, were isolated as the Reineckate. Chromatographic analysis of the Reineckate in acetone solution on alumina showed that only salicifoline was present and no alkaloids other than salicif olive could be recognized.

Note on garnet crystals from Cairnie, Aberdeenshire

In 1938 large crystals of almandine garnet were collected by the writer from a cutting excavated during road-widening operations, on the main Huntly—Keith road, near Cairnie church, about 4½ miles from Huntly. In view of their exceptional size and excellent crystal form, it is felt that the occurrence is worth recording. Garnet crystals of comparable size have been recorded by Heddle from several localities. The Cairnie crystals, considering their size and excellent form, must rank with the finest recorded from Scotland.The rocks at this cutting are coarsely banded garnet-biotite-sillimanite-gneisses with abundant quartz, oligoclase, orthoclase, and biotite, subordinate muscovite, and accessory magnetite, apatite, and zircon. Sillimanite is sporadic in occurrence, forming elongated colourless prisms up to 2 mm. across. The biotite-rich bands generally contain only small garnets, if any, but garnet is very abundant in bands rich in quartz and felspars, and often forms a large part of the rock.

芳香環状異項環の分極 第68報

Heating quinoline-N-oxide with Ac2O at 1 0-140° gives carbostyril with an yield of 20-30%. At the same time, orange-red powder (acetate: colorless prisms, m.p. 330-331°; experimental formula C8H7NO2), a small amount of quinoline and fluorescent yellow needles, (C9H6N)2 0. 1/2 H2O, m.p. 254°, are formed. Similar treatment with Ac2O of 3-, 4-, 5-, 6- and 7-bromoquinoline-N-oxide give corresponding bromocarbostyril with about 70% yield.

Monoacetone Hexuronic Acid

TWENTY grams of hexuronic acid, prepared by Svirbely and Szent-Gyorgyi, were shaken in 500 c.c. of acetone in the presence of 50 grams of anhydrous copper sulphate for twenty-four hours. After filtration, the fluid was evaporated in vacuo to one third of its volume. On addition of a double volume of petroleum ether the monoacetone derivative of hexuronic acid crystallises out in well-formed large, colourless prisms or long needles. These were dissolved in acetone and recrystallised by the addition of petroleum ether. Seventy per cent of the theoretical yield was obtained.

COCAIN IN OTOLOGY AND LARYNGOLOGY.

In 1855 Geadeke isolated a crystalline alkaloid from coca leaves, which he called erythroxylin. Five years later Albert Niemann further investigated this alkaloid and gave it the name cocain. The power of cocain to produce anesthesia was first called attention to by Fronmueller in 1863, but its practical use became more fully known in 1884 through the investigation and experiments of Freud and Koller. It was then first used in ophthalmic surgery. Cocain, like all new or rejuvenated remedies, quickly became a panacea all earthly woes. While it is still largely used for many external and internal lesions, the aurist, laryngologist and gynecologist probably use it with the greater satisfaction, owing to its anesthetic effect upon the mucous membrane. Cocain hydrochlorate, when pure, is found in colorless prisms of strong alkaline reaction, giving an astringent, bitter, burning taste followed by a numbness of the mouth and lips. The folowing

New Compounds of Phosphorus, Nitrogen, and Chlorine

A SERIES of new compounds of phosphorus, nitrogen, and chlorine, and likewise a series of acids derived from them, have been discovered by Mr. H. N. Stokes, and an account of them is contributed to the American Chemical Journal. A familiar compound of the three elements in question, the chlorophos-phuret of nitrogen, discovered by Liebig in 1832, has been the subject of frequent study, and its nature has comparatively recently been very fully demonstrated by Dr. Gladstone. It has been shown, from vapour density determinations, that this remarkably stable compound, which may be distilled in steam and boiled with acids and alkalies without appreciable change, possesses the molecular composition P3N3C16. Mr. Stokes now shows that this substance is only one of a homologous series of compounds having the general formula (PNCl2)n, and that these are the chlorides of a series of acids (PNO2H2)n, which he terms metaphosphimic acids. The second member of the series, (PNC12)4, has been isolated from the product of Dr Gladstone's reaction for the preparation of (PNC12)3, that between phosphorus pentachloride and ammonium chloride; it is a substance almost as stable as the triple compound, and yields on saponification the acid (PNO2H2)4, which is likewise a stable body. Moreover, the acid corresponding to the triple compound has been isolated, and also a higher chloride (PNCl2)x of an oily character, and whose molecular weight has not yet been ascertained. In describing his repetition of Dr. Gladstone's work, Mr. Stokes incidentally mentions the interesting circumstance that the triple compound readily forms enormous crystals, well-developed prisms several inches long and of considerable thickness being frequently deposited from benzene, and indeed their size appears only to be limited by that of the containing vessel and the bulk of solution. These crystals melt at 114°. The quadruple compound melts at I23°˙5, and boils at the normal pressure at 256°˙5. It crystallises well in colourless prisms, which are usually much smaller than those of the triple compound, and exhibit great tendency to develop an a cicular character. It is less soluble in alcohol and benzene than the latter compound; it may be recrystallised from glacial acetic acid, but it exhibits a great aversion for water, not being wet by it, and consequently the crystals float on water. It dissolves in hot concentrated oil of vitriol, but upon boiling most of it sublimes unchanged, an evidence of its great stability. Its vapour is endowed with a pleasant aromatic odour, but inhalation of more than traces is followed in two or three hours by alarming difficulty in breathing and persistent irritation of the air passages. Its vapour density was determined in an atmosphere of hydrogen, and indicated the quadruple formula. Even boiling water exerts only a very slight action upon it; but a smooth decomposition is effected by dissolving in ether, and repeatedly agitating with water. The acid produced is deposited from the water in crystals having the composition (PNO2H2)4 + 2H20. This interesting acid readily decomposes soluble chlorides, nitrates, and sulphates, forming three series of salts, in which respectively one-fourth, one-half, and all the hydrogen is replaced by the metal. The free acid is so highly stable that it may be boiled for hours with nitric acid or aqua regia without decomposition Further details concerning it, and the other compounds isolated, will shortly be published.