到 查阅并下载Collective Volume 3, page 339 ，用碘的丙酮溶液活化（见下文）1. Ordinary copper bronze does not always give satisfactory results in the Ullmann reaction. Moreuniform results are obtained if the copper bronze is prepared as suggested by Kleiderer and Adams.1The copper bronze is treated with 2 l. of a 2% solution of iodine in acetone for 5–10 minutes. Theproduct is then collected on a Büchner funnel, removed, washed by stirring into a slurry with 1 l. of a1:1 solution of concentrated hydrochloric acid in acetone, and again filtered. The copper iodidedissolves, and the copper bronze remaining is separated by filtration and washed with acetone. It is thendried in a vacuum desiccator. It should be used immediately.Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry Volume 3,Issue 4, 1973 选择语言▼ Translator disclaimerSynthesis of Phosphonium Salts of MixedChloro-Bromo Metallate Complexes 1PreviewDownload full text Access optionsDOI:10.1080/00945717308057280John L. Burmeister a , Joel L. Silver a , Edward T. Weleski Jr.a , Edward E. Schweizer a & Charles M. Kopay apages 339-358Publishing models and article dates explained∙Received: 3 Apr 1973∙Accepted: 24 May 1973∙Published online: 06 Dec 2006Synthesis of phosphonium salts of mixed chloro-bromo metallate complexes [求助]Over syntheses in the diphenyl line. [machine translation]和Synthesis in the bip初始悬赏金币40 个mugung11: 取消求助，已退还悬赏金币40 个2014-05-04 15:51作者:Ullmann, F文题:1. Over syntheses in the diphenyl line. [machine translation]和2. Synthesis in the biphenyl series. I期刊名:Berichte der Deutschen Chemischen Gesellschaft期刊年份:1901卷(期),起止页码:34，2174-2185和34，478-480全文链接:https:///scifinder/view/scifinder/scifinderExplore.jsfOrg.Synth,1943,Coll.Vol.2;446[Machine Translation of Descriptors]. By heating up aromatic halogen nitro compounds with copper powder ("copper bronze", see Ber. German Chem. Society 29. 1878; C. 96. II. 533) one receives easy and smooth diphenyl derivative; the reaction occurs also then, if the nitro group does not stand for the halogen is, however, in this case limited to the iodine nitro compounds. At all iodine lets itself take out through copper particularly easily, because the analogous conversion took place also with the iodine benzene, -toluene, -naphthalene, among others. The reaction volume-pulls itself at temperatures of for instance 180-260°; bodies also easily mobile halogen atoms must the vehemence of the effect by diluting with nitrobenzene or causing sand be moderated. Of TAEUBER (Ber. German. Chem. Society 24. 197) 2.2'-dinitrodipheyl already described, NO2. C6H4. C6H4. NO2, formed to 76%, as 5 g whether Rome nitrobenzene in the sulfuric acid bat h on 200° for the theory, warmed up and then 3 g copper-bronze in small helpings under steady accomplish of the mass with the thermometer registered became. For the preparation in larger scales became 30 g o-chloronitrobenzene with 50 g sand on 200-210° he ated up and then 30 g copper so slowly registered that the temperature 250° did not exceed (above 260° decomposing itself the melt lower partial formation of carbazoles); finally still 1/2 hour on 240-245° became heated up and the product then with alcohol or benzene extracts. M-chlorine and m-Bromnitrobenzene were copper not changed by, m-Iodinenitrobenzene (boiling point 278°) supplied with 220-225°, on the other hand easily 3.3' - dinitrodiphenyl, C12H8O4N2; yellow, star shaped grouped needles from tolue ne; melting point 200°; easily soluble into warm benzene, glacial acetic acid; more with difficulty soluble in alcohol (see BRUNNER, WITT, Ber. German. Chem. Ges. 20. 1028). 4.4'-Dinitrodiphenyl, C12H8O4N2, from p-iodine nitrobenzene [KP726, 287° (correcte d)] and copper with 220-235° obtained; yellow needles from toluene; melting point 237° (FITTIG: 233°); few soluble in alcohol; somewhat more easily soluble in benzene. 2.2', 4.4' - tetranitrodiphenyl, (NO2) 2C6H3. C8H5. (NO2) 2, formed by one-hour cooking of 4-Chlor or 4-Brom-l, 3-dinitrobenzol with copper in nitrobenzene; also, as 10 g diphenyls developed in 60 g of nitric acid lower water cooling registered and the red solution, from which crystals of 4-Nitrodiphenyl separated, with weak fuming sulfuric acid (3-4% SO3) were shifted. Yellowish prisms from benzene; melting point 163°; few soluble in alcohol, ether; easily soluble into hot glacial acetic acid, benzene. By registering 10 g m-iodine nitrobenzene in 40 g of nitric acid of the density 1.5 and causing concentrated sulfuric acid, until the liquid became yellow, one receives within 24 hours of 4-Jod-1.2-dinitrobenzol, (NO2) 2C6H3I; yellow crystals from alcohol; melting point 74.5°. Reacted, contrary to analogous chlorine and bromine compound, with co pper with 230 to 250° under formation of 3.3', 4.4'-Tetranitrodiphenyl, C12H8N4; yellow prisms from alcohol; meltingpoint 186°; easily soluble in glacial acetic acid, benzene; somewhat more with difficulty soluble in alcohol, ether; nearly insoluble in ligroin. With the condensation of the picryl chlorides, (NO2) 3C6H2Cl, with copper nitrobenzene or toluene must be added as diluents (in a case, when the toluene was somewhat damp, C6H3 (NO2) 3, appeared as by-product 1.3.5-Trinitrobenzol; lamellas; melting point 121°); when the reagents drying were heated up, took place with about 127° a vehement explosion.2.2', 4.4' 6.6'-hexanitrodiphenyl, (NO2) 3C6H6. C6H2 (NO2) 3, separates from toluene in brownish, thick crystals, the 1/2 mole Toluene contained (escapes with 140°) and with 238° melting; few soluble; solution into concentrated sulfuric acid yellow, in alcohol something ammonia or caustic soda red; not to bring by impact or impact to the explosion. The 1.4-Dihalogen-2-nitrobenzole reacts only with the halogen atom in zero position to the NO2 group. 4.4'-Diechor-2.2-dinitrodiphenyl, NO2. C63Cl. C6H3Cl. NO2, from 1.4-Dichlor-2-nitrobenzol and copper with 240°; yellowish crystals from alcohol, melting point 136°; well soluble into warm alcohol, benzene; few soluble in the ligroin. 4.4'.-.Dibrom-2.2' dinitrodiphenyl, C12H4O4Br2, from 1.4-Dibrom-2-nitrobenzol and copper with 190-225°; yellow needles from alcohol, melting point 138°; easily soluble in benzene, alcohol; few soluble in ligroin. The Bromnitrobenzoe acids supply their copper salts with copper; the esters against it react to quite smoothly under formation of nitrated diphenyldicarbonic acid esters. The esters serving as starting material could be won by introducing HCl into the boiling alcoholic solution acid. 2-Brom-5-nitrobenzoe acid methyl ester, NO2. C6H3Br. COOCH3. Glossy needles from methyl alcohol; melting point 82°; insoluble into cold water; easily soluble in alcohol, ether, benzene. Gave with copper with 180-220° the4.4-Dinitrodiphenyl-2.2' more dicarbonic acid dimethylester, CH3O2C. C6H3 (NO2) . (NO2) C6H3. COOCH3, which SHADWELL from the p, p' -dinitrodiphenic acid, (NO2) (HOOC) C6H3. C6H3 (COOH) (NO2), already represented; yellow small prisms from methyl alcohol; melting point 177°; some water the free acid gave to C14H3O8N2, yellowish needles (from water) of the melting point 248° by 1/2-do-digenetic cooking with concentrated sulfuric acid and 4-Brom-3-nitrobenzoe acid methyl ester, C8H6O4NBr. Glossy needles from methyl alcohol; melting poin t 104°; insoluble in water; few soluble in ligroin, otherwise easily soluble. Reacted with copper with 170-185° under formation of 2.2' dinitrodiphenyl-4.4' more dicarbonic acid dimethylester, C16H12O8N2; yellow prisms from methyl alcohol; melting point 159-160°; easily soluble in glacial acetic acid benzene; more with difficulty soluble into cold; nearly insoluble in ether, ligroin. 4-Chlor-3.5-dinitrobenzoe acid methyl ester, (NO2) 2C6H2Cl. COOCH3. Yellowish needles from methyl alcohol; melting point 175°; few soluble in water, otherwise easily soluble. CH6OOC. resulted in from cooking with copper in nitrobenzene the 2.2',6.6'-Tetranitrodiphenyl-4.4' more dicarbonic acid dimethylester; C6H2 (NO2) 2. (NO2) 2C6H2. COOCH3; needles from little benzene; melting point 173°; few soluble in alcohol; nearly insoluble in ligroin. α-iodine naphthalene becomes from copper bronze with 260-285° to 74% of the theory in 1.1-Dinaphtyl, C10H7. C10H7, transferred; lamellas from alcohol; melting point 155° (corrected); solubl e in cold benzene, boiling ligroin. LOSSEN, LIEBIG's Ann. 141. 79.。