Furthermore benzanilid boils at 160°C. and at such high temperatures as 250°C. and over some of it is apt to be driven off.
(b) 106 grams of benzaldehyde were heated with 93 grams of redistilled aniline at 120°C., for two hours or until the solution was clear. The clear benzalaniline was then poured into 160 grams of selenium dust in a pyrex flask on a sand bath, the flask being connected with an air condenser as before. In order to distribute the flame to better advantage over the bath, an air space was made between the Meker burner and the bath by introducing a wire gauze. Hydrogen selenide was evolved freely. Complete reaction took three days. The extraction and recrystallization were the same as in the former case. The yield was sixty per cent.
The selenazole crystallizes in colorless long needles, melting at 117.5°C. (corr.) Fromm and Martin(58)gave the melting point as 117°C. It is insoluble in water, and in the following solvents it is lightly soluble in the cold, more easily hot: ether, methyl alcohol, acetone, acetic acid, acetic anhydride, chloroform, and nitrobenzene. It is difficultly soluble in ethyl alcohol, ethyl acetate, and carbon tetrachloride, in the cold, but easily soluble hot.
The mononitro derivative of the selenazole, 6-nitro-2-phenylbenzoselenazole, was prepared by nitration with nitric acid at a low temperature:
Twenty-five grams of the selenazole were dissolved in 150 grams of concentrated sulphuric acid, keeping the temperature below the room temperature until complete solution took place. It was then cooled on a freezing mixture and a mixture of sulphuric and nitric acids (previously prepared and cooled by mixing 9.5 grams of nitric and fifteen grams of sulphuric acids) slowly dropped into it in the course of half an hour, using mechanical stirring for four hours. The solution was then poured into two liters of water (ice water), filtered, dried, and recrystallized from acetic acid, and alcohol with the help of animal charcoal. The yield was 95 per cent.
This nitro compound crystallizes in flattened needles of a light yellow color. It melts at 202.4°C. (corr.). It is very insoluble in water; but soluble in hot acetic acid, acetic anhydride, nitrobenzene, nitrotoluene, toluene, benzene, alcohol, and difficultly soluble when cold. The crystals were analyzed and gave the following results,
The conversion of mononitro compound to 6-amino-2-phenylbenzoselenazole was accomplished by the action of tin and hydrochloric acid as follows:
30.3 grams of nitro compound were mixed with 42 grams of twenty mesh tin in a liter flask, immersing the latter in cold water. 175 cc. of conc. HCl were slowly added to the flask. In some cases it was necessary to apply initial heating but when once the reaction started it took place rapidly. After the effervescence had abated, the flask was heated over a free flame, under a return condenser, for two hours. The solution usually turned to a pasty mass, due to the formation of a tin double salt. The mixture was dissolved in a large volume of water and heated on a water-bath, the precipitate filtered out, washed, and preserved. The clear filtrate was treated with concentrated alkali, in excess, the separated amine collected, washed with water, dried and recrystallized from alcohol, using bone-black. The precipitate set aside was treated with strong alkali, the insoluble residue washed, recrystallized, and added to the main product. The yield was 75 per cent.
This amine crystallizes from alcohol in fine yellowish needles, melting at 201.2°-202.3°C (corr.). It is insoluble in water and ether, difficultly soluble in the hot; and fairly soluble in aniline. A pure sample was analyzed and gave the following results:
Five grams of the monoamino compound were mixed with powdered KOH, heated together until the mixture just melted, and maintained in that state for a few minutes. When the latter had cooled down to room temperature, cold water was poured over the mixture. The filtered solution was acidified until no further precipitate was formed. The precipitate was collected and recrystallized from water, m.p. 121°C.
One gram of this solid was placed in a test tube, provided with a cork and a delivery tube, and heated with soda lime; a liquid with the smell of benzene was collected in another test tube cooled with water. When this liquid was treated with a few drops of nitric acid mixture the smell of nitrobenzene was given off. A gram of the crystals was heated with concentrated sulphuric acid and alcohol when the odor of ethyl benzoate was noted.
Five grams of the monoamino selenazole were heated on a water-bath with 10 cc. of acetic anhydride until the solution was clear, which took about two hours. 100 cc. of water were poured into the mixture, which was then neutralized with dilute ammonium hydroxide. The precipitate was filtered, decolorized by animal charcoal, and recrystallized from dilute alcohol.
The acetyl compound, 6-acetamino-2-phenylbenzoselenazole, forms colorless crystals, melting at 188.1°-.7°C. (corr.). It is insoluble in ether, benzene, carbon disulphide; slightly soluble in toluene; soluble in alcohol, ethyl acetate, amyl acetate, acetone, and acetic acid. A pure sample was analyzed and gave the following result,
Five grams of the monoamino compound were dissolved in 200 cc. absolute alcohol with the addition of 3 cc. of benzaldehyde and the clear solution was boiled on a water-bath, with a return condenser, for two hours. After the solution was boneblacked, the yellow precipitate was recrystallized from carbon disulphide. The yield was 90 per cent.
It crystallizes in yellow plates, melting at 156.7°-157.6°C., soluble in benzene, ether, ethyl alcohol, carbontetrachloride, acetone, but difficultly soluble in ligroin. An analysis of the crystals showed the following result,
Five and four tenth grams of the monoamino compound were dissolved in hot conc. HCl, cooled in ice, and diazotized with sodium nitrite solution, until starch iodide paper showed excess nitrous acid. The diazotization was performed in ice, with mechanical stirring, and required about an hour. The diazo solution was poured into a solution of 3 grams B-naphthol in 8 grams of NaOH and 60 cc. of water, while gradually stirring. A very deep red solution formed. This was acidified with excess HCl, salted out by NaCl, and crystallized from aniline-alcohol mixture. In the pure state, it is a deep red powder, with a metallic lustre when rubbed, melting at 284.2°C. An analysis showed the following result,
The nitration for the production of dinitro derivative was at first carried out under the same conditions as in the preparationof mononitro compound and after the latter was formed more nitric acid mixture was added with the addition of heat: conc. sulphuric acid, keeping it below room temperature. It was then cooled in a freezing mixture and half the volume of a nitric acid mixture (prepared and cooled by mixing 19 grams of nitric and 30 grams of sulphuric acids) was introduced very slowly to the selenazole solution through a dropping funnel, maintaining at this temperature for two hours (using mechanical stirring). The remaining half of the nitric acid mixture was then slowly introduced and the flask was heated on a water-bath for two hours. The solution was poured into two liters of water, the precipitate filtered off, dried and recrystallized several times from acetic acid. The yield was 80 per cent.
This dinitro compound crystallizes in fine yellow needles, m. p., 246.8°C. (corr.), very insoluble in water, but soluble in hot acetic acid, acetic anhydride, nitrobenzene, nitrotoluene, ethyl alcohol, and difficultly soluble cold. It was analyzed and the following results were found,
The conversion of the dinitro to diamino derivative was accomplished in the same manner as the reduction of the mononitro derivative excepting that twice as much tin and HCl were used.
This diamino compound crystallizes in yellowish glistening needles from alcohol and pyridine; m. p., 269°-270.5°C.; was analyzed and gave the following results,
The diacetyl and dibenzylidene compounds were also prepared from these diamino derivatives. The former crystallizes in cubes from dilute alcohol; m. p., 307°C (Corr.) and the latter in beautiful yellow plates from carbon disulphide, m. p., 195°-196°C. (Corr.). An analysis of these two compounds showed the following results,
Both the monoamino and the diamino derivatives form intensely colored dyes when diazotized and coupled with phenols and aromatic amines. The dyes formed are fast to light. In the following table silk is given to represent the fabrics used. Wool and cotton were dyed similar shades, though with slight variation. Each silk sample was dyed in acid or alkaline baths as indicated and each bath contained 0.01 gram in twenty cc. solution:
Yü-Gwan Chen was born in Nanking, China, March 8, 1893. After graduation from college in 1915, he further studied Chinese classics, 1915-16. He entered Case School of Applied Science, Cleveland, Ohio, as a special student in the Department of Chemistry, 1916-17. He registered at Columbia University to pursue graduate work in chemistry under the Faculty of Pure Science; and was awarded the degree of Master of Arts in 1918. From September 1919 to June 1922, he has been pursuing research in organic chemistry in the research laboratories of Havemeyer Hall, Columbia University.
FOOTNOTES:[A]Not a new compound but prepared by a different method.[B]Note—dimethyl selenophene, however, is colorless.
[A]Not a new compound but prepared by a different method.
[A]Not a new compound but prepared by a different method.
[B]Note—dimethyl selenophene, however, is colorless.
[B]Note—dimethyl selenophene, however, is colorless.
Transcriber's notes:The diagram of 3-(p-phenylarsonic)-aminoselenazine, labelled (II), has been adjusted to make its structure clearer.The "l" in "2HCl" in the first equation under "Preparation of 2-methyl-4-selenoquinazolone" was missing in the original.The following is a list of changes made to the original. The first line is the original line, the second the corrected one.selnoquinazoloneprepared in the course of this researchselenoquinazoloneprepared in the course of this researchon four different strains of mousecarcenomaand one strainon four different strains of mousecarcinomaand one strainin consequence of its smell I so completelylossmy sense of smellin consequence of its smell I so completelylostmy sense of smellof the phenazine,oxasine, thiazine, acridine series showof the phenazine,oxazine, thiazine, acridine series showandSeagain most powerful of the whole series.and:Seagain most powerful of the whole series.simplicity, is that ofBabrieland Stelzner(52),simplicity, is that ofGabrieland Stelzner(52),on cooling was filtered out andrecrystalizedfrom dilute alcohol.on cooling was filtered out andrecrystallizedfrom dilute alcohol.a sealed tube at 110° with alcohol saturated at zerodegreewitha sealed tube at 110° with alcohol saturated at zerodegreeswithIt was prepared fromSodiumhydroxide in absolute alcoholIt was prepared fromsodiumhydroxide in absolute alcoholtook an hour andhalf. The flask was removed from the oiltook an hour anda half. The flask was removed from the oilTheprecipitratewas recrystallized several timesTheprecipitatewas recrystallized several times(e) An attempt was made to make o-aminobenzselenamide,(e) An attempt was made to make o-aminobenzoselenamide,It dissolves readily inalkaliesand is slightly solubleIt dissolves readily inalkalisand is slightly solubleThis was found to be desirable when thedinitroselezazolewas burned.This was found to be desirable when thedinitroselenazolewas burned.into a large volume of water when theselenozoleprecipitated outinto a large volume of water when theselenazoleprecipitated outit was necessary to dissolve in hot HCl again and torecrystalize.it was necessary to dissolve in hot HCl again and torecrystallize.(b) 106 grams ofbenaldehydewere heated with 93 grams of(b) 106 grams ofbenzaldehydewere heated with 93 grams ofIt isdifficultysoluble in ethyl alcohol, ethyl acetate, andIt isdifficultlysoluble in ethyl alcohol, ethyl acetate, andtoluene, benzene, alcohol, anddifficultysoluble when cold.toluene, benzene, alcohol, anddifficultlysoluble when cold.from alcohol in fine yellowish needles, melting at201.2°202.3°Cfrom alcohol in fine yellowish needles, melting at201.2°-202.3°Ccarbontetrachloride, acetone, butdifficultysoluble in ligroin.carbontetrachloride, acetone, butdifficultlysoluble in ligroin.19 grams of nitric and 30 grams of sulphuricacidswas introduced19 grams of nitric and 30 grams of sulphuricacids)was introducedin the same manner as the reduction of mononitro derivativein the same manner as the reduction ofthemononitro derivativeThis diamino compoundcrystalizesin yellowish glistening needlesThis diamino compoundcrystallizesin yellowish glistening needlescompounds were also prepared fromthisdiamino derivatives.compounds were also prepared fromthesediamino derivatives.The formercrystalizesin cubes from dilute alcohol;The formercrystallizesin cubes from dilute alcohol;
The diagram of 3-(p-phenylarsonic)-aminoselenazine, labelled (II), has been adjusted to make its structure clearer.
The "l" in "2HCl" in the first equation under "Preparation of 2-methyl-4-selenoquinazolone" was missing in the original.
The following is a list of changes made to the original. The first line is the original line, the second the corrected one.
selnoquinazoloneprepared in the course of this researchselenoquinazoloneprepared in the course of this research
on four different strains of mousecarcenomaand one strainon four different strains of mousecarcinomaand one strain
in consequence of its smell I so completelylossmy sense of smellin consequence of its smell I so completelylostmy sense of smell
of the phenazine,oxasine, thiazine, acridine series showof the phenazine,oxazine, thiazine, acridine series show
andSeagain most powerful of the whole series.and:Seagain most powerful of the whole series.
simplicity, is that ofBabrieland Stelzner(52),simplicity, is that ofGabrieland Stelzner(52),
on cooling was filtered out andrecrystalizedfrom dilute alcohol.on cooling was filtered out andrecrystallizedfrom dilute alcohol.
a sealed tube at 110° with alcohol saturated at zerodegreewitha sealed tube at 110° with alcohol saturated at zerodegreeswith
It was prepared fromSodiumhydroxide in absolute alcoholIt was prepared fromsodiumhydroxide in absolute alcohol
took an hour andhalf. The flask was removed from the oiltook an hour anda half. The flask was removed from the oil
Theprecipitratewas recrystallized several timesTheprecipitatewas recrystallized several times
(e) An attempt was made to make o-aminobenzselenamide,(e) An attempt was made to make o-aminobenzoselenamide,
It dissolves readily inalkaliesand is slightly solubleIt dissolves readily inalkalisand is slightly soluble
This was found to be desirable when thedinitroselezazolewas burned.This was found to be desirable when thedinitroselenazolewas burned.
into a large volume of water when theselenozoleprecipitated outinto a large volume of water when theselenazoleprecipitated out
it was necessary to dissolve in hot HCl again and torecrystalize.it was necessary to dissolve in hot HCl again and torecrystallize.
(b) 106 grams ofbenaldehydewere heated with 93 grams of(b) 106 grams ofbenzaldehydewere heated with 93 grams of
It isdifficultysoluble in ethyl alcohol, ethyl acetate, andIt isdifficultlysoluble in ethyl alcohol, ethyl acetate, and
toluene, benzene, alcohol, anddifficultysoluble when cold.toluene, benzene, alcohol, anddifficultlysoluble when cold.
from alcohol in fine yellowish needles, melting at201.2°202.3°Cfrom alcohol in fine yellowish needles, melting at201.2°-202.3°C
carbontetrachloride, acetone, butdifficultysoluble in ligroin.carbontetrachloride, acetone, butdifficultlysoluble in ligroin.
19 grams of nitric and 30 grams of sulphuricacidswas introduced19 grams of nitric and 30 grams of sulphuricacids)was introduced
in the same manner as the reduction of mononitro derivativein the same manner as the reduction ofthemononitro derivative
This diamino compoundcrystalizesin yellowish glistening needlesThis diamino compoundcrystallizesin yellowish glistening needles
compounds were also prepared fromthisdiamino derivatives.compounds were also prepared fromthesediamino derivatives.
The formercrystalizesin cubes from dilute alcohol;The formercrystallizesin cubes from dilute alcohol;