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Volume 34, Issue 7
Displaying 1-11 of 11 articles from this issue
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Renji OKAZAKI1976 Volume 34 Issue 7 Pages 439-454
Published: July 01, 1976
Released on J-STAGE: January 22, 2010
JOURNAL FREE ACCESSThe chemistry of o-quinonoid compounds is described with emphasis on recent advances. This review covers o-quinodimethanes, o-quinonemethides, o-quinonemethideimines, o-thioquinonemethides, and o-quinonediimines. No mention is made on o-quinones and heteroaromatic compounds with o-quinonoid structure.View full abstractDownload PDF (1537K) -
Kiyonori SHINODA1976 Volume 34 Issue 7 Pages 455-465
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSIt has recently been spoken that the exposure to vinyl chloride may cause both genetic damage and birth defect as well as increase in liver cancer. The destruction of the earth's protective ozone layer by chlorofluorocarbons has become a heated topic in scientific and political circles.
This review is designed primarily to obtain the information on the reactions of chloroalkanes which are somewhat troublesome as mentioned before. In order to understand better the effect of structure on reactivity and properties of chloroalkanes, the chemistry of chloroalkanes subdivided into chlorination, chlorine-sensitized photooxidation, dehydrochlorination and nucleophilic substitution.
The reactivity of chloroalkane towards various reagents is affectcted by the electronic character of the attacking reagent and the substituent effect of substrate. The following reactions are facilitated by the electron-releasing substituent : chlorination, chlorine-sensitized photooxidation, catalytic dehydrochlorination on solid acid, solvolysis, Menschutkin reaction and pyrolysis in the gas phase. On the other hand, the rates of dehydrochlorination with alkali, co-pyrolysis with alcohols and reduction of chlorine atom with hydrosilanes or organotin hydrides are increased by the electron-withdrawing inductive effect of substituent.View full abstractDownload PDF (1613K) -
Atsushi TAKADA1976 Volume 34 Issue 7 Pages 466-476
Published: July 01, 1976
Released on J-STAGE: January 22, 2010
JOURNAL FREE ACCESSMany color reaction of organic componnds in Brønsted or Lewis acid medium which have been used for the detection and the determination of biological materials or for organic analyses are well known. In this review, some of the reaction mechanisms of these coloration, the coloration of aromatic aldehyde with electrophilic reagent in sulfuric acid such as the de Fazi reaction and the Molisch reaction, the coloration of cholesterol in strong acid such as the Liebermann-Burchard reaction, the Zak reaction, the Hirschsohn reaction, the Mueller reaction and the reaction of cholesterol with benzoyl peroxide, the coloration of sexual hormone in acid such as the Kober reaction, the Mueller reaction of estrone and the reaction of teststerone, the Carr-Price reaction, and the Marquis reaction, were reviewed. Among them, the most of coloration using sulfuric acid or other protic acid as the reaction medium were ascribed to carbocation formation, while the color in the Molisch reaction and the Marquis reaction might arise from cation-radical, and the colorations in antimonyl trichloride reagent were ascribed to cation-radical formation.View full abstractDownload PDF (1505K) -
Toshihiko MIGITA1976 Volume 34 Issue 7 Pages 477-487
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe review covers some examples in which dichotomy between “radical” and “polar” path can not completely be demonstrated. Some cases in which radical and polar fission of bonds seem to occur through common intermidiates are found in thermolysis of certain acylperoxides and aliphatic chlorination catalyzed by olefin or PCl5. On the other hand, formation of bonds between some nucleophiles and electrophiles involve radical intermediates through electron transfer processes or via complex intermediates. These examples can be found in nucleophilic substitutions (SRN1 of aliphatic and aromatic substrates, Williamson type SN, action of some nucleophiles on peroxides) and nucleophilic additions of organometallic reagents to carbonyl compounds.View full abstractDownload PDF (1651K) -
Synthesis of 6, 7-Benzomorphan Derivatives From Amino Acids. IVKentaro TAMAKI, Naoki NAITO, Kyoichi FUJII1976 Volume 34 Issue 7 Pages 488-491
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe reaction of 6-ethoxy-2-benzylamino-1- (p-methoxyphenyl) -3, 4-dimethyl-3-hexanol (4), the intermediate of the synthesis of 6, 7-benzomorphan derivatives from tyrosine, with various acids were investigated.
Next results were obtained.
1) The reaction of 4 with boron trifluoride-etherate-acetic acid or 85% phosphoric acid at reflux temperature gave 2- {1-benzylamino-2- (p-methoxyphenyl)} ethyl-2, 3-dimethyl tetrahydrofuran (6).
2) Heating in 47% hydrobromic acid, 4 gave 2- {1-benzylamino-2- (p-hydroxyphenyl)} ethyl-2, 3-dimethyl tetrahydrofuran, which was cyclized to 1-benzyl-2- (p-hydroxybenzyl) -3, 4-dimethyl-3-piperidinol by the reaction with boron tribromide.
3) The reaction of 4 with boron tribromide-pyridine in methylene dichloride gave 6 and 2-p-anisy1-1-benzyl-3, 4- dimethyl-3-piperidinol.View full abstractDownload PDF (504K) -
Koji ISOGAI, Toshio OGINO, Takeshi HIIRO, Kazuyoshi ENDO, Nobuyasu YOK ...1976 Volume 34 Issue 7 Pages 492-498
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSLiquid phase catalytic hydrogenolysis of straight-chain 1, 2-epoxyalkanes to primary alcohols was studied over nickel-phosphorus catalyst.
Propylene oxide (1) was hydrogenolyzed mainly to 1-propanol (6a) and 2-propanol (6b) accompanied with propane (8) and alcoholysis products (7) of (1). The selectvity for (6a) was 8690% under the following conditions ; 0.1 mol of (1), 100210°C, 4060 kg/cm2 of initial hydrogen pressure and 0.12.0 g of catalyst. 1, 2-Epoxyhexene (2), 1, 2-epoxyoctane (3), 1, 2-epoxydecane (4) and 1, 2-epoxydodecane (5) were also hydrogenolyzed selectively to the corresponding primary alcohols. At 130145°C and 40 kg/cm2, using 0.1 g of catalyst for 0.05 mol of epoxide, the products, hydrocarbon (mol%) and total alcohol (mol%), and ratio of primary to secondary alcohol were, respectively, as follows ; (2); 9.5, 90.5, 89.0 : 11.0, (3); 11.6, 88.4, 91.2 : 8.8, (4); 15.3, 84.6, 89, 6 : 10.4, (5); 11.1, 88.9, 86.3 : 13.7.
Hydrogenolysis of (2) in the presence of sodium hydroxide, triethylamine, pyridine or sodium iodide increased the amount of 2-hexanol (9b). Especially, the addition of sodium iodide increased the yield of (9b) remarkably and the formation of a little amount of 2-hexanone (11) was observed.View full abstractDownload PDF (957K) -
Sadayoshi FURUMOTO1976 Volume 34 Issue 7 Pages 499-502
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSN, N'-Dicyclohexylformamidine (DCFA) was allowed to react with N-bromosuccinimide (NBS) at room temperature in the presence of pyridine to give N, N' -dicyclohexylcarbodiimide (DCC) in 61% yield. An equimolar amount of DCFA and bromine was allowed to react and successively treated with 10% aqueous NaOH to give DCC (78%). On the other hand, DCC was also obtained when DCFA was treated with sodium hypochlorite, 1-chlorobenzotriazole or trichloroisocyanuric acid in the presence of 10% aqueous NaOH. DCFA (1 mol) was allowed to react with NBS (1/2 mol) to give DCFA-HBr salt (44%) and DCC (26%). Similar reaction of DCFA (1 mol) with bromine (1/3 mol) was carried out to give DCFA-HBr salt (54%) and DCC (18%). 1 : 1 Addition product was formed when DCFA-HBr salt was treated with an equimolar amount of bromine and on treatment with 10% aqueous NaOH, 1 : 1 addition product afforded DCC in 72% yield.View full abstractDownload PDF (595K) -
The Synthetic Reactions of Aliphatic Nitro Compounds. XEisuke KAJI, Shiro SAKAI, Shonosuke ZEN1976 Volume 34 Issue 7 Pages 503-504
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe alkylation reaction of nitroacetate (1) with some p-substituted benzyl halides (2) in dipolar aprotic solvent such as dimethylacetamide, led to β- (p-substituted phenyl) -α-hydroxyiminopropionic sters (5; p- substituted groups : H, Cl, NO2 and CH3) in reasonable yields. The reaction mechanism was also elucidated.View full abstractDownload PDF (279K) -
Masao ITO1976 Volume 34 Issue 7 Pages 505-511
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSMaleic Anhydride is produced through an oxidation in a catalytic vapor phase of various hydrocarbons, and Benzene and C4 Hydrocarbons are usually its feedstock in commercial production.
A catalyst having vanadium oxides as an active component acts an important role in the process of oxidating hydrocarbons into Maleic Anhydride. In order to find out a catalyst having a higher selectivity against Maleic Anhydride, a study on the oxigen transfer mechanism over the surface of catalyst in the course of oxidation procedure was first carried out, and the oxidation kinetics was also developed for determing the optimum conditions for reation.
Process for commercial purpose employs two types of reactor ; one being a fixed bed type and the other a fluidized bed type. In the following, comparison of these two types and characteristic features of several commercial processes for Maleic Anhydride production are also dealt with.View full abstractDownload PDF (1131K) -
Mataro TANEDA1976 Volume 34 Issue 7 Pages 512-514
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSDownload PDF (484K) -
[in Japanese], [in Japanese]1976 Volume 34 Issue 7 Pages 515
Published: July 01, 1976
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESS
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