Volume 1

Watts' dictionary of chemistry / revised and entirely rewritten by H. Forster Morley and M.M. Pattison Muir ; assisted by eminent contributors.

Date:: 1888-1894

Credit: Watts' dictionary of chemistry / revised and entirely rewritten by H. Forster Morley and M.M. Pattison Muir ; assisted by eminent contributors. Source: Wellcome Collection.

Provider: This material has been provided by the Royal College of Physicians of Edinburgh. The original may be consulted at the Royal College of Physicians of Edinburgh.

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$CuH8N20 [190°]. Needles. V. sol. water or alco- hol, si. sol. ether or benzene. It is probably . CMe^ CH3.C<f ^CH. \N:C(OH)/ Propionamidine forms a homologue, methyl- ethyl-oxy-pyrimidine [160°]. Its hydrochloride forms thick prisms, C7H10N.,OHC1 [c.243°]. V. e. sol. water, v. sol. alcohol—(C7H10N,OHCl),PtCl4 [236°]. Prisms. (Pinner, B. 17, 2520 ; 18,2847). 26. With urea in alcoholic solution it forms /3-uramido-crotonic ether (Behrend, A. 229, 5): MeC(OH) :CH.CO,Et + NH.,.CO.NH2 = NH2.CO.NH.CMe: CH.CO,Et + H20. The free /3-uramido-crotonic acid, when liberated from its salts, changes at once into its anhydride, methyl-uracil: NH.CO.NH.CMe: CH.CO 27. Thio-urea (40 g.), heated with aceto-acetic ether (40 g.) slowly to 150°, gives a compound C5H6N2OS (5 g.), which may be thio-methyl- uracil. It may be crystallised from water. It dissolves in alkalis and is reppd. by acids. Its melting-point lies above 300°. Its aqueous solution gives with AgN03 an amorphous pp. of C,H1Ag.,N2SO (Nencki a. Sieber, J. pr. [2] 25, 72). If a little HC1 be added to an alcoholic solution of thio-urea and aceto-acetic ether, un- stable needles are formed. These are converted by alcoholic potash into potassium thio-methyl- uracil, C5H5KN2SO (List, B. 19, 219). 28. Aceto-acetic ether (20 g.), phenyl-urea (10 g.), and ether (6 g.) at 150° react thus : C6H,0O3 + C7H8N20 = C13H,cN203 + H20. The product is an oil which is decomposed by alcoholic potash with formation of ammonia and aniline, and by boiling cone. HC1 with form- ation of CO,, alcohol, acetone, and phenyl- carbamic ether, PhNH.C02Et. The reactions indicate that the body C13H1(iN,03 has the consti- tution NPhH.CO.N : CMe!CH,C02Et, or perhaps /NH\ CO< >CMe.CH2.CO,Et \NPh' (Behrend, A. 233, 1). 29. Combines directly with diphcnyl-urea, in presence of a little ether at 150°, forming an oil, CH)H2.,N204. This body is converted by al- coholic KOH into aniline and K2C03, and by acids into phenyl-carbamic ether and aniline. The body must be PhNH.CO.NPh.C(OH)Me.CH2.C02Et. Similar addition products are probably first formed in the case of other ureas, but H20 splits off: PhNH.CO.NH.C(OH)Me.CH,.CO.,Et = H20 + PhNH.CO.N: CMe.CH2.C02Et. 30. p-Di-azo-toluenc Chloride, acting on an alcoholic solution of aceto-acetic ether, forms yellow needles of ^-toluene-azo-aceto-acetic ether [188°] CcH4Me.N,.CH(CO.CH3).C02Et (Eichtera. Miinzer, B. 17, 1929 ; v. azo compounds). 31. Hydrazo-benzene at 100°-150° forms HOEt and a crystalline base, C16H,4N20 (A. Miiller, B. 19, 1771). 32. Copper aceto-acetic ether is converted by COCl2 into an anhydride of di-acetyl-acetone di-carboxylic ether, CO(CHAc.C02Et)2. The .anhydride may be: CH3.C - O - C.CH3 II II CO,Et.C-CO-C.CO,Et. [80°]. Sol. glacial HOAc, H2S04, cone. HC1, ben- zene, alcohol, or ether. NH3 converts this body into oxy-di-methyl-pyridine-di-carboxylic ether: CH3.C-NH-C.CH3 II II CO,Et.C-CO-C.C02Et (Conrad a. Guthzeit, B. 19, 22). 33. Aceto-acetic ether, heated with CS2 and PbO at 100°, forms ' thio-carbonyl-aceto-acetic ether' CH3.CO.C(CS).C02Et [156°-162°]. Yellow needles (from alcohol) (Norton a. Oppenheim, B. 10, 703). 34. S2C12 converts sodium aceto-acetic ether suspended in benzene into sulphido-aceto-acetio ether S(CHAc.C02Et)., [81°] (Buchka, B. 18, 2092). 35. With succinic acid it reacts thus : C6H10O3 + C4H604 = C10H12O5 + 2H20. The product is a crystalline acid [76°], which is the acid ether of a dibasic acid C8HuCv [200°] (Fittig, B. 18, 2526). Condensation products from aceto-acetic ether. —1. By heat: Passed through a red-hot tube it forms dehydro-acetic acid (q. v.) and other products (Perkins, jun. C. J. 47, 240).—2. By hydrochloric acid : Dry HC1 at 8° forms, in four weeks, acetic ether and ' carb-aceto-acetic ether ' C8H1„O3(290o-295°uncor.). S.G. 221-136. This liquid is slightly decomposed on distillation. It gives no colour with aqueous Fe2Cl6 (Duisberg, A. 213,179). Carb-aceto-acetic ether is also formed when aceto-acetic ether is heated with acetyl chloride at 120° (Wedel, A. 219, 116).—3. By sulphuric acid: C6H7(OH)(C02H).CO.O.C6H7(C02H)(C02Et) [62°]. Got by leaving a mixture of aceto-acetic ether (1 pt.) and cold cone. H2S04 (2| pts.) for fourteen days and then pouring into water (Hantzsch, A. 222, 4). Needles resembling as- bestos. SI. sol. cold water, m. sol. hot water and ether, v. sol. alcohol, v. e. sol. chloroform. De- composed by heat. It is acid to litmus and, when hot, has a spicy odour. Its formation may be represented thus: 4C(iHI0O3 = C18H220„ + 3C2H5OH. Reactions.—(a) Boiling alkalis form carbonate and acetate, acetone, and mesityl oxide. (b) On neutralising with alcoholic potash it decomposes thus: C„H,(OHXC02H ).C0.0.C,H7(C03H)C0;1Bt + EOH= C0H,(C02K)/ >+C8H,(C02Et)< >+2HaO, the potassium salt of mesitene-lactone carb- oxylic acid being ppd. while its ether remains in solution. Mesitene-lactone Carboxylic Acid CH3.C:C(C02H).CMe:CH.CO.O [155°] (iso-dehydracetic acid). Fluffy crystals (from water). SI. sol. cold water, v. sol. hot water. Monoclinic prisms (from alcohol). May be sublimed. Reactions.—Distilled with lime it gives mesi- tyl oxide. Salts.—KA'iaq. — NaA'.— NH4A'— BaA'2.— MgA'2.-CuA'22aq.—Ag4H3A'7.-Ag6HA'7. Strong$