Micro-Dumas method of nitrogen determination was revised to give improved results. In this revised method, the sample is weighed in a platinum boat, the combustion tube of quartz having a side tube is used, and the movable furnace is operated automatically. By these improvements, the burning procedure becomes rapid and simplified. By preventing the adherence of bubbles on the mercury surface in the azotometer, pretreatment of marble and hydrochloric acid, and by the control of the process by open-type mercury pressure gauge, microbubble procedure has been made more accurate and rapid. The present method is especially adapted for use with variety of samples, the error being within ±0.2%. The total time required for analysis is approximately 1hour per sample, in continuous operation.
A method whereby carbon, hydrogen and sulfur could be determined in one operation was devised by the combination of Stragand's method of sulfur determination with the existing carbon and hydrogen determination. The burning and catalytic systems were separated from the nitrogen fixation, ground joint being used for joining these two tubes which would eliminate the necessity of the use of a grease, and the procedure of the handling of silver wire was simplified. For samples not containing nitrogen, the analysis could be carried out by attaching a simple lead tube at the ground joint portion. The time of analyses and the amount of sample needed can be reduced to one-half that by the existing method and the whole procedure has been extremely simplified. The error on each element is within ±0.2%.
As an example of water-soluble papaverine-like compounds possessing two hydroxyls in the phenyl ring in 1-position, two out of six theoretically possible derivatives were prepared as 1-(2′, 4′-dihydroxyphenyl)- and 1-(3′, 4′-dihydroxyphenyl)-3-methyl-6, 7-methylenedioxyisoquinoline. Benzylation was attempted in order to protect the hydroxyl in the β-resorcylic acid, but the objective 2, 4-dibenzyloxybenzoic acid could not be obtained and in its stead, a mixture of several compounds were obtained. Acetylation was then carried out, followed in the ordinary manner to chloride, amide and the isoquinoline cyclization which was attended by deacetylation by which the first compound was obtained. For the preparation of the latter, dibenzylprotocatechualdehyde was oxidized with hydrogen peroxide, followed through carboxylic acid, chloride and amide to 1-(3′, 4′-dibenzyloxyphenyl) derivative which was catalytically reduced to a phenolic base but this compound was very unstable and became resinous.
As one of water-soluble papaverine-like compounds, 1-(3′-methoxy-4′-hydroxybenzyl)-3-methyl-6, 7-methylenedioxyisoquinoline was prepared. Vanillin benzyl ether was led to azlactone, then to 3-methoxy-4-benzyloxyphenylacetic acid, which was condensed with amine as its chloride, and finally by isoquinoline cyclization to the objective compound. This substance is identical with a compound obtained from 4-benzyloxybenzoic acid which was led to an amide by the Arndt-Eistert reaction and cyclized. The compound is obtained as colorless prismatic crystals of m.p. 237°, and forms a hydrochloride of m.p. 265-266° (decomp.), and a picrate of m.p. 199-200° (decomp.).
As a preliminary examination of the physiological action of 6, 7-dimethoxy-3-benzyl-isoquinoline, 1-phenyl-3-benzylisoquinoline was prepared. Chalcone was chosen as the starting material and two methods were attempted. One was to lead it to α-methoxy- or α-hydroxy-β-benzamido-α, γ-diphenylpropane, followed by cyclization, and the other a cyclization of β-benzamido-α, γ-diphenylpropane, to 1-phenyl-3-benzyl-3, 4-dihydroisoquinoline which was dehydrogenated to the objective compound. The former method, lacking the alcoxyl group in the aromatic nucleus, failed to undergo isoquino-line cyclization although the reaction was carried out under fairy vigorous conditions and yielded an oxazoline derivative of m. p. 143-143.5°. The latter method yielded a syrupy isoquinoline compound which gave a platinate of m. p. 211-213° (decomp.). The latter clearly forms an isoquinoline compound as there is no fear of the formation of an oxazoline, and since the product differs from that obtained by the former method, it is seen that this method is not suitable.
It was found that 1-substituted 3-methyl-6, 7-methylenedioxy-3, 4-dihydroisoquinoline is obtained by heating a mixture of 1 mole each of safrol and acid amide in benzene or toluene with the addition of an excess of phosphoryl chloride. For example, use of acetamide, benzamide or phenylacetic amide as the acid amide respectively yields 1-methyl-, 1-phenyl- or 1-benzyl-3-methyl-6, 7-methylenedioxy-3, 4-dihydroisoquinoline. This method of isoquinoline synthesis is attended with a poor yield and the presence of a methyl group in the 3-position but if these points could be improved, it would offer an interesting synthetic procedure for 3-methyl-3, 4-dihydroisoquinoline derivatives since there is no necessity of preparing an amide as by the existing method.
Examination of in vitro antibacterial power of isonicotinylglycine hydrazide against tubercle bacilli showed that the compound also possessed a fair amount of antibacterial action against human tubercle bacilli and, therefore, such actions were examined with various hydrazides. The samples were divided into aliphatic, aromatic, and heterocyclic compounds, and few of each group were tested. Special attention was paid to compounds containing glycine and it was found that the antibacterial action of heterocyclic compounds, especially those of pyridine series, were found to be the greatest. Aromatic compounds were found to be the next, and the aliphatic compounds possessed a very weak action. The culture medium used was a modified Kirchner medium and the strains used were H37Rv, Aoyama B, Takagaki and H2 strains of human type, Minowa strain of bovine type, and Takeo strain of avian type tubercle bacilli.
By the high pressure catalytic reduction of phenylacetone and dimethylamine, with a nickel catalyst, dl-1-phenyl-2-dimethylaminopropane was obtained in 58% yield. This was resolved into optical isomers, using tartaric acid, to d-1-phenyl-2-dimethylaminopropane hydrochloride, m. p. 182-183°, [α]D16+13.1°, and l-compound, m. p. 182-183°, [α]D16-13.1°.
The optically active 1-phenyl-2-dimethylaminopropane was led to optically active 1-phenyl-2-dimethylaminopropane methiodide by the ordinary method and then to optically active methochloride. It was then confirmed that the l-1-phenyl-2-dimethylaminopropane methiodide and methochloride derived from the d-compound possessed the same steric configuration as that of natural ephedrine, i.e. they belonged to the L-typebased on alanine. A few theoretical considerations were proposed for the optical rotation of the 1-phenyl-2-aminopropane homologs, in comparison with the norephedrine homologs.
The pentacyano-iron complex salts, such as sodium nitroprusside, sodium pentacyano-amminferroate and sodium pentacyanoaquoferroate, react with aromatic primary amines and some R-NH-CS-NH-R′ type compounds, such as aromatic thiosemicarbazones, thiocarbanilides, and p-ethoxyphenylthioureas, in caustic soda solutions, in the presence of hydrogen peroxide, to give green coloration. The procedure is as follows: To a very small amount of the sample are added 5 drops of 2.5% solution of sodium nitroprusside, 1% solution of sodium pentacyanoamminferroate or 1% solution of sodium pentacyanoaquoferroate, 2 drops of 35% hydrogen peroxide, and 3 drops of 1N sodium hydroxide, and the mixture is heated in a boiling water bath. Green coloration is also developed by reacting sodium nitroprusside and sodium azide, in the phosphoric acidity, to aromatic primary amines and R-NH-CS-NH-R′ type compounds, and rendering the mixture alkaline with sodium hydroxide. This method can also be used to estimate qualitatively the aromatic primary amines and some compounds of R-NH-CS-NH-R′ type.
Some time ago, thiochrome (II) was obtained by the application of esterification agent to 3-[2′-methyl-4′-aminopyrimidyl- (5′)]-methyl-4-methyl-5-β-hydroxyethylthiazol-2-thione (I), the reaction of which was assumed to pass through an intermediate state of thioether compound (III). In the present series of experiments, (II) was obtained by treating with hydrochloric acid after heating ethyl or benzyl N-[2-methyl-4-aminopyrimidyl-(5)]-methyldithiocarbamate (IV, R=C2H5 or C6H5⋅CH2-) and γ-aceto-γ-chloro-propyl acetate (V) in formic acid. In this reaction, also, it is assumed that an intermediate thioether compound (VI) is first formed which undergoes cyclization to form a thiochromine nucleus. Previously, (II) had also been obtained by the application of mercuric chloride and sodium bicarbonate to (I). Since 3-[2′-methyl-4′-hydroxypyrimidyl-(5′)]-methyl-4-methyl-5-β-hydroxyethyl-thiazol-2-thione (IX) does not seem to change by the same treatment, it seems more rational to assume that mercuric chloride and sodium bicarbonate act as dehydrogen sulfide agent to promote the reaction of (I) to (II).
1) By the application of sodium butoxide to 3-nitro- and 6-nitro-4-chloroquinaldines, corresponding 4-butoxy derivatives were obtained. Nitration of 4-butoxyquinaldine with nitric acid or nitric and sulfuric acids resulted in the formation of 6-nitro-4-butoxy-quinaldine, whose reduction gave 6-amino derivative. Condensation of the latter with chloroacetyl chloride yielded 6-chloroacetylamino derivative and application of diethylamine to the latter gave 6-diethylaminoacetylamino-4-butoxyquinaldine. 2) Reduction of 3-nitro-4-butoxyquinoline to 3-amino compound, its condensation with chloroacetyl chloride to obtain 3-chloroacetylamino derivative and subsequent application of diethylamine yielded 3-diethylaminoacetylamino-4-butoxyquinoline.
1) 4-Hydroxyquinoline-3-carboxylic ester and 4-hydroxy-6-ethoxyquinoline-3-carboxylic ester were changed to 4-chloro derivatives by treatment with phosphoryl chloride, and sodium methoxide or butoxide were applied to give 4-methoxy or -butoxy derivatives. These 4-alcoxyquinoline-3-carboxylic esters formed 3-carboxamides by the action of methanolic ammonia. 2) 4-Chloro-6-ethoxyquinoline-3-carboxylic ester changed to 3-carboxamide by the action of methanolic ammonia, and the condensation of sodium methoxide changed it to the 4-methoxy compound. 3) By the condensation of diethylaminoethylamine to 4-methoxy- or 4-butoxy-quinoline-3-carboxylic ester yielded diethylaminoethylamides. 4-Methoxyquinoline-3-carboxylic diethylamide was prepared by changing 4-hydroxyquiuoline-3-carboxylic acid to 4-chloro carboxylic chloride, reacted with diethylamine to form 3-carboxylic diethylamide and then reacted with sodium methoxide.
O- and N-acylates and O, N-diacylate of p-sulfamylbenzyl alcohol were prepared and O→N acyl rearrangement was attempted but no such rearrangement took place. Antibacterial activities against Staphylococcus aureus, Escherichia coli, and human type Mycobacterium tuberculosis were tested but the majority failed to show any efficacy. However, O, N-dibenzoate did show a weak efficacy against all the bacteria tested, especially against human tubercle bacilli.
In the previous report, intramolecular rearrangement of 5-aminoisoxazoles, possessing lower alkyl substituents in the 3- and 4-positions, by heating to imidazolone-(2) was described, and the possibility of such arrangement was examined with 17 kinds of 5-aminoisoxazoles in the present series of experiments. 3-Methyl-4-propyl-(IV), 3-butyl-4-propyl-(V), 3-phenyl-4-methyl-(VI), and 3-methyl-4-benzyl-5-aminoisoxazoles (VII), all undergo rearrangement and urea was found to be a good catalyst. No such rearrangement occured in 3-methyl-(XIV), 3-phenyl-(XV), 3-tolyl-(XVI), 3-benzyl-4-phenyl-(XVII), 3-methyl-4-phenyl-(XVIII), 3, 4-diphenyl-(XIX), and 3, 4-tetrame-thylene-5-aminoisoxazoles (XX). In this arrangement, an intermediate of the following structure is assumed to be formed: R-C(NH2)=CR′-C=O and R-C (NH2)=CR′-N=C=O
2-Acetamido-4-methyl-5-thiazolyl alkyl sulfides (VII) and sulfones (VIII) were synthesized by routes shown in Chart 1 (b, c, d, e). In this reaction, halogenation of alkyl acetonyl sulfides (IV) gives α-halogen compounds (V), and, under some specific conditions, the sulfones (XI) also yield α-halogen compounds (XII), which condense with thiourea to form thiazole nucleus possessing alkyl sulfides and sulfones in the 5-position. Oxidation of alkyl acetonyl sulfides (IV), differing from that of aryl acetonyl sulfides, does not form (XI) but yields alkyl methyl sulfones (IX). In reaction (d), X1 of m. p. 191° and acetate of m. p. over 350° are invariably obtained as by-products, whose structures are now under examination. Antibacterial tests of (VII) and (VIII) are given in Table I.
By improving the Wohl-Aue method of synthesizing phenazines, o- or p-nitroanisole and aniline were reacted with potassium hydroxide in toluene solution by which 1-me-thoxy- or 2-methoxy-phenazine was prepared, demethylation of which yielded 1-hydroxy- or 2-hydroxy-phenazine. To reverse the nitro and amino groups, o- or p-anisidine was reacted with nitrobenzene by which, besides the objective compounds, phenazine N-mono-oxide in which the methoxyl group had disappeared was obtained from the ortho compound, and 2-methoxyphenazine N-monoxide in the case of para compound.
Fungistatic and sporostatic effects of 14 kinds of essential oils, such as cassia, laurel, fennel, kobus and terpentine oils, were examined against some pathogenic fungi, such as Epidermophyton, Achorion and Trichophyton, in which order some inhibitory effects were found to exist. Especially, the effect was strong in cassia, laurel and fennel oils and the growth inhibitory action of these oils against six different kinds of fungi was tested but no great difference was found to exist. The fungi do not easily acquire resistance. The effect of serum was found to decrease fungistasis by one-half, and sporostasis by one-quarter. Growth inhibitory action against Gram-positive bacteria, such as tubercle bacilli and staphylococci, was effective, but that against Gram-negative, such as dysentery and coli bacteria, was ineffective except in cassia and fennel oils.
Fungistatic effect of 20 kinds of salicylaldehyde, benzaldehyde, and nitrof urfurol derivatives was found to be effective in that order. The growth inhibitory action was found to be powerful when the aldehyde radical was free, and in oxime and anil forms. Acquisition of resistance against these compounds by the fungi was found to be difficult.
1) Nitration of phenyl pyridyl-(2) ether with sulfuric and nitric acids gives 2, 4-dinitrophenyl compound when the reaction is carried out at above 50° and a 4-nitrophenyl compound when reacted at 30-35°. Application of piperidine to these nitrophenyl pyridyl-(2′) ethers results in decomposition to form nitrophenylpiperidines. 2) By the condensation of alkali salts of o-, m- and p-nitrophenol to 2-bromopyridine, 2-, 3- and 4-nitrophenyl pyridyl-(2′) ethers were respectively obtained. 3) Application of hydrogen sulfide to 4-nitrophenyl 5′-nitropyridyl-(2′) ether in alcoholic ammonia solution results in its reduction to 4-nitrophenyl 5′-aminopyridyl-(2′) ether. The latter, by diazotization and deamination, changes to 4-nitrophenyl pyridyl-(2′) ether. Catalytic reduction of 4-nitrophenyl 5′-nitropyridyl-(2′) ether with palladium-carbon yields 4, 5′-diamino derivative. 4) 4-Amino (acetamino) phenyl 5′-nitropyridyl-(2′) ethers were prepared by the condensation of 2-chloro-5-nitropyridine and alkali salt of p-amino- or p-acetaminophenol.
By the condensation of 2-chloro-3(5)-nitropyridines, 2, 3-dichloro-5-nitropyridine and 2-nitro-5-bromopyridine with alkali salts of thiophenol or chloro- or nitro- thiophenols, chloro- or nitrophenyl. 3(5)-nitropyridyl-(2) thioethers, chlorophenyl 3-chloro-5-vitro-pyridyl-(2) thioethers, and 2, 5-dichlorophenyl 2′-nitropyridyl-(5′) thioether were prepared. Reduction of these nitropyridyl thioethers yielded corresponding aminopyridyl thioethers.
Diarylarsinic acids were easily reduced to the corresponding diarylarsinous acids with mineral acid in the presence of a small amount of potassium iodide. By this procedure, many diarylarsinous acids were readily obtained in pure state.
In order to decrease the toxicity of diarylarsinous acids, several compounds containing -SH were combined with diarylarsinous acids into diarylthioarsinites, which are new substances of interest as antibacterial drugs.
1) It was clarified that the titration of formaldehyde is possible by the cyanogen bromide method. This titration method can be used even in the presence of Cl′, Br′, S″, SO4″, S2O3″, or organic substances, as long as the bromide or the oxidation product does not liberate iodine by hydrogen iodide. 2) Titration is carried out by preparing a standard solution of potassium cyanide, which is calibrated by the cyanogen bromide method. A definite volume of the sample solution is placed in a glass-stoppered bottle, a definite excess volume of potassium cyanide standard solution (volume corresponding to sodium thiosulfate standard solution-a cc.) added, allowed to stand for 5minutes, acidified with 20% phosphoric acid, allowed to stand for 15minutes after the addition of excess of bromine solulion and phenol, excess of solid potassium iodide added and allowed to stand for 30minutes. The liberated iodine is then titrated with sodium thiosulfate standard solution, using starch test solution as the indicator (volume of sodium thiosulfate standard solution required-b cc.). The amount of formaldehyde in the sample is calculated from the following equation: HCHO (mg.)=(a-b) f (mg.) where f is the amount of HCHO corresponding to 1 cc. of the standard solution of sodium thiosulfate.
The fusion of ω-benzamidoacetophenone with a mixture of thiourea and iodine results in the formation of a thiazole ring and a 2, 5-diaminothiazole derivative, 2-amino-5-benzamido-4-phenylthiazole, in a quantitative yield. Such 2-amino-5-acylaminothiazole derivatives obtained are new substances, only a few 2, 5-diacylamino- and 2-acylamino-5-aminothiazole derivatives being known.
By the catalytic reduction of nitrohippuric acid and its esters using Raney nickel as a catalyst, 2-, 3- and 4-aminohippuric acids and their esters were obtained. Of these amino compounds, amino and carboxyl could not be detected from the 2-aminohip-puric acid which was assumed to be due to the formation of a lactim or a lactam by the liberation of one mole of water. One mole of 4-nitrohippuric acid forms a molecular compound, m. p. 250° (decomp.), with 1 mole of its potassium salt, and one of m. p. 190-192° with 1 mole of sodium salt.
By the method of preparing thiosemicarbazone derivatives by the application of thiosemicarbazide to aldazine in glacial acetic acid, thiosemicarbazones of benzaldehyde, furfural, salicylaldehyde, anisaldehyde, p-tolylaldehyde, m-tolylaldehyde, o-, m- and p-nitrobenzaldehyde, 5-nitrofurfural, p-hydroxybenzaldehyde, p-dimethylaminobenzaldehyde, resorcylaldehyde, piperonal, vanillin, and o-aminobenzaldehyde were obtained. This reaction does not proceed smoothly in alcoholic solution. The application of hydrazine to 2-methyl-4-amino-5-formylpyrimidine in aqueous solution does not yield an azine componnd but invariably forms a monohydrazone.
It was concluded from experimental results as outlined below that the lowering of calcium content in rabbit serum by the crude pepsin products was not due to pepsin itself. 1) Crystalline pepsin does not show any effect on the serum calcium level. 2) The dialyzate, which does not possess proteolytic activity, obtained from crude pepsin also shows the action of calcium decrease. 3) Acid extract of gastric membrane possesses the power to decrease serum calcium level, both in fractions possessing strong and weak action of protein decomposition.
After treatment of hog stomach membrane with cold 80% acetone at pH 8.0 for a short time, extraction with water of pH 8.0, and repeated precipitation at isoelectric point (pH 5.4) yields the so-called pH 5.4-Precipitate which possesses the power to lower calcium level in rabbit serum. This lowering action is non-diffusible and is lost by heating. Similar pH 5.4-Precipitate obtained from the intestinal membrane also possesses the power to lower calcium level though much weaker than that of. the precipitate obtained from the gastric membrane.
As one method of utilizing the levulic acid obtained as a by-product of amino acidd industry, synthesis of a perfume was attempted. Starting with ethyl levulate and isoamyl bromide, 4, 7-dimethyl-1, 4-octanolide was obtained by the Grinard reaction, and subsequent ring cleavage, dehalogenation, esterification and reduction yielded the isomer of the objective citronellol, 4, 7-dimethyl-3-octan-1-ol (isocitronellol). This was confirmed by deriving it to the semicarbazone, m. p. 86-88°, of levulic ester.
As a result of examination of the synthetic reaction to obtain isocitronellol (4, 7-dimethyl-3-octan-1-ol) from levulic acid, it was found that the object can be achieved by the following two routes. One is the reduction of the lactone (4, 7-dimethyl-1, 4-octanolide) to glycol with subsequent dehydration, while the other is the ring cleavage of the lactone with hydrogen chloride and ethanol, followed by dehydrochlorination to unsaturated ester, and finally by the Bouveault-Blanc reduction, the respective yield being 14% and 16.5% of the theoretical amount. The formation of isocitronellol from glycol by the first method is accompanied by the formation of 2-methyl-2-isoamyltetrahydrofuran, which is present in the perfume and greatly detracts its aroma, that this method was found to be highly undesirable.
In order to comparatively examine their cholinergic action, 22 kinds of compounds listed in Table I were prepared. The action was found to be especially strong when the alkyl in the alkyltrimethylammonium halide possessed 4 to 6 carbons, the action decreasing rapidly above and below this number. With the alkyls possessing 4-6 carbons, the cholinergic action was found to decrease in the quarternary salts if the methyl chain was situated near the nitrogen in the ammonium. The phenylalkyltrimethylammonium halides, in which the side-chain alkyl group consisted of 0-3 carbons, also showed similar cholinergic action. Of those compounds, the phenylpropyl derivative showed adrenal action, as well as the cholinergic. The phenylalkyl derivatives possessing alkyl group consisting of 4-5 carbons showed a strong adrenal action, without any appearance of a cholinergic action. 4-Methyl-5-dimethylaminomethylimidazole methiodide, whose structure is similar to that of histamine showed only 1/100 the cholinergic action of the former.
Twenty-nine kinds of styryl-type dyes were synthesized by the condensation of aromatic aldehydes or 5-nitrofurfural to the quaternary salts of 6-dimethyl-or-diethyl-aminoquinaldine in alcoholic or acetic anhydride solution. Condensation in alcohol necessitated the use of piperidine as the condensing agent.
1) Eight kinds of aminovinyl compounds were prepared by the condensation of various diphenyl or dipyridyl formamidines to the respective quaternary salts of quinaldine, 6-diethylaminoquinaldine, and 4-ethylpyridine. By the application of p-acetaminobenzene sulfochloride to several of the aminovinyl compounds, some compounds containing p-acetaminobenzenesulfamino group were obtained. 2) By the application of p-dimethylaminobenzaldehyde or p-dimethylaminocinnamic aldehyde to 6-chloro (nitro, dimethylamino, diethylamino)-quinaldines, 2, 3, 5, 6-tetramethylpyrazine, 4-nitro-2, 6-lutidine-N-oxide, quinaldine-N-oxide and 2, 3, 5, 6-tetramethyl-pyrazine-N, N′-dioxide, corresponding p-dimethylaminostyryl and p-dimethylaminocin-namylidenemethyl compounds were obtained.
Several kinds of p-amino-p′-alcoxybenzil compounds were prepared by the hydrolyzation of 4-amino-4-alcoxyisonitrosodesoxybenzoin, which was easily obtained by the reduction of 4-nitro-4-alcoxyisonitrosodesoxybenzoin with ammonium sulfide. Attempt to obtain the objective by the reduction of the corresponding nitro compounds was unsuccessful due to the decomposition by reducing agents to α-diketones.
p-Amino-p′-hydroxybenzil was prepared from p-nitro-p′-ethoxybenzil which was converted first to p-nitro-p′-hydroxybenzil with aluminum chloride, then to a monoxime with hydroxylamine hydrochloride, reduced with ammonium sulfide to p-amino monoxime, and finally hydrolyzed to the α-diketone. p-Amino-p′-methylbenzil was obtained according to the method described in the previous report from 4′-nitro-4-methyl-desoxyben-zoin obtained by the Friedel-Crafts' condensation of p-nitrophenacetyl chloride with toluene.
In experiments to observe the effect of three principles of fertilizers on the alkaloid formation of Datura Tatula L., it had been found that the effect of nitrogen wes very great, especially the fact that of NH4-N being greater than that of NO3-N. As a result of further experiments on the relationship between the alkaloid formation or absorptive power of various nitrogen and the effect of the addition of NO3-N and NH4-N, under various acidity of soil, it was found that the soil of pH 5.3-5.9 seemed to be best suited both for growth and crop yield. In the area given NO3-N, the effect of soil acidity seemed to be comparatively small, the growth being approximately uniform, whereas the area provided with NH4-N, the effect was remarkable, the growth being seen only on the soil of pH 5.3 and 5.9. The componental yields of the alkaloid, total nitrogen, pure protein nitrogen, water-soluble protein nitrogen, and non-protein nitrogen were higher in the area provided with NH4-N than with NO3-N, the highest being in the area of pH 5.3 [Ca(OH)2 25g./pot], where about one-half of the nitrogen supplied had been absorbed by the leaves. The nitrogen that forms alkaloid is only 0.07-0.09% of NH4-N supplied, or 0.04-0.07% of NO3-N.
Application of γ-aceto-γ-chloropropyl acetate (II) (R=COCH3) or alcohol (II) (R=H) to ammonium N-[2-methyl-4-aminopyrimidyl (5)]-methyl-dithiocarbamate (I) results in the respective formation of corresponding dithiourethane (III) (R=COCH3 or H). The free carbamic acid (IV) is obtained by the application of the calculated amount of hydrochloric or acetic acid to (I). (IV) also reacts with (II) to form the hydrochloride (VI) of dithiourethane. Application of an equimolar amount of carbon disulfide to 2-methyl-4-amino-5-aminomethylpyrimidine results in the formation of the pyrimidine salt (V) instead of (IV). The application of (II) necessitates heating since neither (I) nor (IV) is soluble in the solvents, thereby permitting the formation of 2-thio-7-methyl-1, 2, 3, 4-tetrahydropyrimido (4, 5-d) pyrimidine (VII) as a by-product. The sodium salt (VIII) of the carbamic acid, obtained by the addition of an equimolar amount of sodium hydroxide to (I), (IV), and (V), results in facile reaction with (II) because (VIII) is easily soluble in water, and (III) is obtained in a good yield, without the formation of (VII) as a by-product. α-Methyl-α-ethoxy-β-chlorotetrahydrofuran (IX) is less reactive and hardly reacts with (I), (IV), (V), and (VIII), but yields γ-aceto-γ-chloropropyl alcohol (II) (R=H) when warmed with water and undergoes reactions as outlined above.
The Leuckart reaction effects reductive amination of aldehydes or ketones with formamide or ammonium formate. It has been found that a mixture of urea and formic acid can be used in place of formamide or ammonium formate, and this modified procedure was found to give better results as compared to the usual method. Experimenal data are given in the accompanying Table.