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Organic microsynthesis
131
ABSTRACTS ucts obtained by the action of alkali metal chlorate, bromate, perchlorate on 200-mg. quantities of V203 is reported.
iodate, periodate,
or
Preparation of chromium(~ll)-tris(8-amino-ethylate), A. Kiintael and H. Trabitzsch; Z. unurg. u. allgem. Chem., 299, 188-196 (1959). Preparation and purification of red crystalline Cr(OCH&H,NH& for microscopic investigation is described. On the reaction IlNb + Z&O2 + 6NbO + NbsSi3, H. Schafer and K. D. Dohmann, Z. anorg. u. allgem. Chem., 299, 197-202 (1959). The preparation of Nb&& by heating 400 mg. Nb powder and SiO, in a sealed evacuated quartz tube at 8001000” for several days is described. Preparative studies with lower niobium chlorides, H. Schafer and K. D. Dohmann, Z. arwrg. u. allgem. Chem., 300, l-32 (1959). Preparations of decigram quantities of niobium chlorides in a sealed tube are described.
Organic Microsynthesis Synthesis of da-methyl-ALsteroids. The interrelationships of cholesterol, citrostdienol, and lophenol, Y. Mazur and F. Sondheimer, J. Am. Chem. Sot., 80,629699 (1958). Descriptions are given of the modification of the Wolff-Kishner reduction, oxidation, and ozonolysis procedures for use with 15-500 mg. of steroid. and structure of the Co, unsaturated fatty acids in menhaden body oil, W. Stoffel and E. H. Ahrens, Jr., J. Am. Chem. Sot., 80,6604-6608 (1958). Adaptations of oxidation and reductive ozonolysis procedures for 25-100 mg. fatty acid are des,cribed.
Isolation
The synthesis of d-(Ghydroxy-d-methoxy-S,(t-methylene dioxyphenyl)-benzojuran, a new compound from yeast, A. F. Wagner, A. N. Wilson, and K. Folkers, J. Am. Chem. Sot., 81, 5441-44 (1959). Fusion of 16 mg. of 2-(2methoxy-3,4-methylenedioxyphenyl)3-nitrofuran, 125 mg. of KOH, and 2 drops of water in a gold crucible at 230” yields 4.8 mg. product after purification. (See specifically p. 5444.)
Reaction of diazomethane with A%!?O-ketosteroids, H. L. Slates and N. L. Wendler, J. Am. Chem. Sot., 81, 5472-75 (1959). KMn04 and 050a oxidation, maleic anhydride addition, formylation, and isomerization of IO-100-mg. quantities of the ketosteroids are described. Thiohydantoins. Part IV, J. T. Edward and S. Nielsen, J. Chem. Sot., 1959,232731. Oxidation and acid and alkaline hydrolysis of decigram quantities of thiohydantoins are reported.
132
ABSTRACTS
The condensation of l-acetylcyclohexene with R-methylcyclohexanone, E. R. Clark, J. Chem. Sot., 1959, 234447. Reduction with LiAlH4 and NaBH4 of 218400 A 70-mg. sample of crystalline mamg. of the organic compounds is described. terial sublimed into the air condenser was recovered and recrystallized. Part II. The synthesis of some S’-indolylbenzoHeterocyclic compounds of nitrogen. &nones, J. M. Bruce, J. Chem. Sot., 1959,2366-75. Dlazotization, amalgamated zinc wool reduction, sodium iodate oxidation, decigram quantities of nitrogen heterocyclics are described. of Ionization constants of heterocyclic substances. Part III. Mercapto-derivatives pyridine, guinoline, and isoquinoline, A. Albert and G. B. Barlin, J. Chem. Sot. 1959, 2384-296. Methylation of di-S-quinolyl disulfide (100 mg.) with 0.08 ml. CH31 in 3 ml. CHIOH heated at 100” for 8 hr. gave 100 mg. dark brown crystals. (See specifically p. 2395.) Cyclic amidines. Part IX, K. Butler and M. W. Partridge, J. Chem. Sot., 1959, 2396-2400. 2-o-Aminophenyl-6-oxo-4,5-benz-l,3-oxazine (600 mg.) and anthranilamide (340 mg.), when heated together at 100’ for 8 days, afforded 90 mg. of 4hydroxyquinazoline as a sublimate. (See specifically p. 2399.) 6-Aminomethylene-i ,%o?imethylbarbituric acids, J. W. Clark-Lewis and M. J. Thompson, J. Chem. Sot., 1959, 2401-2408. Preparations on a decigram scale of 5-aminomethylene-1,3-dimethylbarbituric acids are described. The isolation and structure of geigerinin, a guaianalide, J. P. D. Villiers, J. Chem. Sot., 1959, 2412-14. Dehydrogenation of 75 mg. geigerinin gave 19 mg. blue oil which afforded 5 mg. of the adduct with 1,3,5-trinitrobenzene. Ozonolysis of 500 mg. geigerinin gave 113 mg. product (20yo yield) after steam distillation. A synthesis of a-diketones, A. M. Cragg, F. M. Dean, and G. Winfield, J. Chem. Sot., 1959, 2431-32. Solution of 500 mg. of 3,Pdiphenylcyclopentanon~1,2dione in acetone and oxidation with potassium permanganate in sulfuric acid gives y-0x0-& r-diphenylbutyric acid. Isolation of oxo-steroids under neutral conditims, W. Taylor, Nature, 182, 1735 (1958). Oxosteroids are separated from a mixture (10 mg.) with other steroids by formation of the Girard complex in ethanol solution in the presence of a cation exchange resin and subsequent splitting of the complex with formaldehyde. Brominatiun of nucleic acids and their derivatives, A. S. Jones and D. L. Woodhouse, Nature, 183, 1603-1605 (1959). Nucleic acids (0.1 mg.) are brominated in water or hydrochloric acid (O.lN) at room temperature. Ultraviolet spectra indicate resistance of adenine and its derivatives to bromination; this may be used as a method for specific degradation of nucleic acids. Potassium permanganate was found to be a better reagent for determination of adenine in deoxyribonucleic acid. MICROCHEMICAL
JOURNAL,
VOL.
IV,
ISSUE
1
ABSTRACTS
133
Microchemical-organic reactions on glass fiber paper, V. Prey and A. Kobil, Osterr, Ch.emiker-Ztg., 59,260-62 (1958). The advantages of glass paper as a supporting medium for chemical reactions are described. The sample is placed upon the glass fiber paper and the reagent, such as a strong base, acid, or oxidizing agent, is added. Purification of folic acid, W. Sakami and R. Knowles, Science, 129, 274 (1959). Cellulose column chromatography followed by filtration through charcoal gives folic acid with a negative Bratton-Marshall test and absence of fluorescence spots on paper chromatograms.
Micro Apparatus and Miscellaneous Tools Construction of thread-type salt bridge and immersiollrtype, silver-silver chloride electrode, J. T. Stock, Chemist Analyst, 48, 8-9 (1959). An asbestos-thread type of salt bridge which can be made part of an integrated design for an immersion silversilver chloride electrode and salt bridge for potentiometry is described. Expedient for microfiltration, J. M. Corliss, Chemist Analyst, 48, 16 (1959). A modification is made in the filtration apparatus for gravimetric micro analysis. Adhering particles and plugged filters can be overcome by manipulation of the attached syringe. All-glass pressure regulator, N. B. Mehta, Chemist Analyst, 48, 16-17 (1959). A sensitive and inexpensive manostat in which an increase or decrease in a reduced pn:ssure can be effected while in operation can be constructed as illustrated. Multiple sample continuous dialyzer, J. B. Stark, Chemist Analyst, 48, 17 (1959). The multiple samples are placed in individual, seamless cellophane tubes. These are tumbled inside a 5-gal. bottle of circulating water. Either the dialyzed or residual fraction is collected. Test-tube adapter for Beckman DU spectrophotometer, B. Zak and L. A. Williams, Ch,emist Analyst, 48, 17-18 (1959). A test-tube adapter made from a wooden block permits determination of the absorption value of each of the layers of a twophased colored derivative. Rotating sample table for multiple polarographic analyses, J. Luck, Chemist Analyst, 48, 18 (1959). Illustrations are given for the construction of a rotating table suitable for multiple polarographic analysis from three aluminum disks or other material. Visualization of end point color changes in titrimetry, J. E. Bolzan, Chemist Analyst, 48, 18 (1959). The color change is observed in the narrow band of immiscible solvent (heavier than water) obtained by inverting the stoppered volumetric flask.
ABSTRACTS ucts obtained by the action of alkali metal chlorate, bromate, perchlorate on 200-mg. quantities of V203 is reported.
iodate, periodate,
or
Preparation of chromium(~ll)-tris(8-amino-ethylate), A. Kiintael and H. Trabitzsch; Z. unurg. u. allgem. Chem., 299, 188-196 (1959). Preparation and purification of red crystalline Cr(OCH&H,NH& for microscopic investigation is described. On the reaction IlNb + Z&O2 + 6NbO + NbsSi3, H. Schafer and K. D. Dohmann, Z. anorg. u. allgem. Chem., 299, 197-202 (1959). The preparation of Nb&& by heating 400 mg. Nb powder and SiO, in a sealed evacuated quartz tube at 8001000” for several days is described. Preparative studies with lower niobium chlorides, H. Schafer and K. D. Dohmann, Z. arwrg. u. allgem. Chem., 300, l-32 (1959). Preparations of decigram quantities of niobium chlorides in a sealed tube are described.
Organic Microsynthesis Synthesis of da-methyl-ALsteroids. The interrelationships of cholesterol, citrostdienol, and lophenol, Y. Mazur and F. Sondheimer, J. Am. Chem. Sot., 80,629699 (1958). Descriptions are given of the modification of the Wolff-Kishner reduction, oxidation, and ozonolysis procedures for use with 15-500 mg. of steroid. and structure of the Co, unsaturated fatty acids in menhaden body oil, W. Stoffel and E. H. Ahrens, Jr., J. Am. Chem. Sot., 80,6604-6608 (1958). Adaptations of oxidation and reductive ozonolysis procedures for 25-100 mg. fatty acid are des,cribed.
Isolation
The synthesis of d-(Ghydroxy-d-methoxy-S,(t-methylene dioxyphenyl)-benzojuran, a new compound from yeast, A. F. Wagner, A. N. Wilson, and K. Folkers, J. Am. Chem. Sot., 81, 5441-44 (1959). Fusion of 16 mg. of 2-(2methoxy-3,4-methylenedioxyphenyl)3-nitrofuran, 125 mg. of KOH, and 2 drops of water in a gold crucible at 230” yields 4.8 mg. product after purification. (See specifically p. 5444.)
Reaction of diazomethane with A%!?O-ketosteroids, H. L. Slates and N. L. Wendler, J. Am. Chem. Sot., 81, 5472-75 (1959). KMn04 and 050a oxidation, maleic anhydride addition, formylation, and isomerization of IO-100-mg. quantities of the ketosteroids are described. Thiohydantoins. Part IV, J. T. Edward and S. Nielsen, J. Chem. Sot., 1959,232731. Oxidation and acid and alkaline hydrolysis of decigram quantities of thiohydantoins are reported.
132
ABSTRACTS
The condensation of l-acetylcyclohexene with R-methylcyclohexanone, E. R. Clark, J. Chem. Sot., 1959, 234447. Reduction with LiAlH4 and NaBH4 of 218400 A 70-mg. sample of crystalline mamg. of the organic compounds is described. terial sublimed into the air condenser was recovered and recrystallized. Part II. The synthesis of some S’-indolylbenzoHeterocyclic compounds of nitrogen. &nones, J. M. Bruce, J. Chem. Sot., 1959,2366-75. Dlazotization, amalgamated zinc wool reduction, sodium iodate oxidation, decigram quantities of nitrogen heterocyclics are described. of Ionization constants of heterocyclic substances. Part III. Mercapto-derivatives pyridine, guinoline, and isoquinoline, A. Albert and G. B. Barlin, J. Chem. Sot. 1959, 2384-296. Methylation of di-S-quinolyl disulfide (100 mg.) with 0.08 ml. CH31 in 3 ml. CHIOH heated at 100” for 8 hr. gave 100 mg. dark brown crystals. (See specifically p. 2395.) Cyclic amidines. Part IX, K. Butler and M. W. Partridge, J. Chem. Sot., 1959, 2396-2400. 2-o-Aminophenyl-6-oxo-4,5-benz-l,3-oxazine (600 mg.) and anthranilamide (340 mg.), when heated together at 100’ for 8 days, afforded 90 mg. of 4hydroxyquinazoline as a sublimate. (See specifically p. 2399.) 6-Aminomethylene-i ,%o?imethylbarbituric acids, J. W. Clark-Lewis and M. J. Thompson, J. Chem. Sot., 1959, 2401-2408. Preparations on a decigram scale of 5-aminomethylene-1,3-dimethylbarbituric acids are described. The isolation and structure of geigerinin, a guaianalide, J. P. D. Villiers, J. Chem. Sot., 1959, 2412-14. Dehydrogenation of 75 mg. geigerinin gave 19 mg. blue oil which afforded 5 mg. of the adduct with 1,3,5-trinitrobenzene. Ozonolysis of 500 mg. geigerinin gave 113 mg. product (20yo yield) after steam distillation. A synthesis of a-diketones, A. M. Cragg, F. M. Dean, and G. Winfield, J. Chem. Sot., 1959, 2431-32. Solution of 500 mg. of 3,Pdiphenylcyclopentanon~1,2dione in acetone and oxidation with potassium permanganate in sulfuric acid gives y-0x0-& r-diphenylbutyric acid. Isolation of oxo-steroids under neutral conditims, W. Taylor, Nature, 182, 1735 (1958). Oxosteroids are separated from a mixture (10 mg.) with other steroids by formation of the Girard complex in ethanol solution in the presence of a cation exchange resin and subsequent splitting of the complex with formaldehyde. Brominatiun of nucleic acids and their derivatives, A. S. Jones and D. L. Woodhouse, Nature, 183, 1603-1605 (1959). Nucleic acids (0.1 mg.) are brominated in water or hydrochloric acid (O.lN) at room temperature. Ultraviolet spectra indicate resistance of adenine and its derivatives to bromination; this may be used as a method for specific degradation of nucleic acids. Potassium permanganate was found to be a better reagent for determination of adenine in deoxyribonucleic acid. MICROCHEMICAL
JOURNAL,
VOL.
IV,
ISSUE
1
ABSTRACTS
133
Microchemical-organic reactions on glass fiber paper, V. Prey and A. Kobil, Osterr, Ch.emiker-Ztg., 59,260-62 (1958). The advantages of glass paper as a supporting medium for chemical reactions are described. The sample is placed upon the glass fiber paper and the reagent, such as a strong base, acid, or oxidizing agent, is added. Purification of folic acid, W. Sakami and R. Knowles, Science, 129, 274 (1959). Cellulose column chromatography followed by filtration through charcoal gives folic acid with a negative Bratton-Marshall test and absence of fluorescence spots on paper chromatograms.
Micro Apparatus and Miscellaneous Tools Construction of thread-type salt bridge and immersiollrtype, silver-silver chloride electrode, J. T. Stock, Chemist Analyst, 48, 8-9 (1959). An asbestos-thread type of salt bridge which can be made part of an integrated design for an immersion silversilver chloride electrode and salt bridge for potentiometry is described. Expedient for microfiltration, J. M. Corliss, Chemist Analyst, 48, 16 (1959). A modification is made in the filtration apparatus for gravimetric micro analysis. Adhering particles and plugged filters can be overcome by manipulation of the attached syringe. All-glass pressure regulator, N. B. Mehta, Chemist Analyst, 48, 16-17 (1959). A sensitive and inexpensive manostat in which an increase or decrease in a reduced pn:ssure can be effected while in operation can be constructed as illustrated. Multiple sample continuous dialyzer, J. B. Stark, Chemist Analyst, 48, 17 (1959). The multiple samples are placed in individual, seamless cellophane tubes. These are tumbled inside a 5-gal. bottle of circulating water. Either the dialyzed or residual fraction is collected. Test-tube adapter for Beckman DU spectrophotometer, B. Zak and L. A. Williams, Ch,emist Analyst, 48, 17-18 (1959). A test-tube adapter made from a wooden block permits determination of the absorption value of each of the layers of a twophased colored derivative. Rotating sample table for multiple polarographic analyses, J. Luck, Chemist Analyst, 48, 18 (1959). Illustrations are given for the construction of a rotating table suitable for multiple polarographic analysis from three aluminum disks or other material. Visualization of end point color changes in titrimetry, J. E. Bolzan, Chemist Analyst, 48, 18 (1959). The color change is observed in the narrow band of immiscible solvent (heavier than water) obtained by inverting the stoppered volumetric flask.