Muller, Ann., 1864, 131, p. 35 2), and by the action of silver oxide on s-di-chloracrylic ester .at 125° C. (0.
Its ethyl ester condenses with hydrazine to form pyrazolone (R.
It is the methyl ester of a neutral body colchicein, which may be obtained in white acicular crystals.
It is a most important synthetic reagent; with sodium or sodium ethylate it forms sodio-malonic ester, which reacts readily with alkyl halides, forming alkyl malonic esters, which are again capable of forming sodium derivatives, that by further treatment with alkyl halides yield the di-alkyl malonic esters.
Held synthesized the acid from ethyl chlor-acetoacetate (from chlorine and acetoacetic ester) by heating with potassium cyanide and saponifying the resulting nitrile.
Perkin, junr., in 1883, that ethylene and trimethylene bromides are capable of acting in such a way on sodium acetoacetic ester as to form triand tetramethylene rings.
CH :CH (OH), formed by acting on formic ester with acetone in the presence of sodium ethylate, readily yields [1.3.51-triacetylbenzene, C 6 H 3 (CO CH 3) 3; oxymethylene acetic ester or formyl acetic ester or ß-oxyacrylic ester, (HO)CH :CH CO 2 C 2 H 51 formed by condensing acetic ester with formic ester, and also its dimolecular condensation product, coumalic acid, readily yields esters of [1.3.
We may here mention the synthesis of oxyuvitic ester (5-methyl-4-oxy-I-3-benzene dicarboxylic ester) by the condensation of two molecules of sodium acetoacetic ester with one of chloroform (Ann., 1883, 222, p. 249).
OH COOH,when acetoneoxalic ester, CH 3 CO CH 2 CO CO CO 2 C 2 H 5, is boiled with baryta (Ber., 1889, 22, p. 3271).
This compound is converted by chlorine water into octachloracetylacetone (3) by methyl alcohol into the ester of dichlormalonic acid and tetrachioracetone (4); whilst ammonia gives dichloracetamide (5) (Th.
Willstatter (Ber., 1900, 33, p. 1164) obtained this acid by the action of a methyl alcoholic solution of ammonia on dibrompropylmalonic ester at 140° C., the diamide formed being then hydrolysed either by hydrochloric acid or baryta water: CH 2 CBr(C02H) 2 CH 2.
Knorr, by the action of ammonia on aceto-acetic ester, obtained (3-imidobutyric ester, which with nitrous acid yields a-isonitroso-(3-imidobutyric ester, CH 3 C(:NH) C(:N OH) CO 2 C 2 H 5.
Reduction of this ester leads to the formation of ammonia, hydroxylamine, and dimethyl pyrrol dicarboxylic ester, C(CH3): C C02R HN< C(CO 2 R) :C CH3.
He also found that diaceto succinic ester reacts with compounds of the type NH 2 R(R = H, CH 3, OH, NHC 6 H 5, &c.) to form pyrrol derivatives CH3 CO CH CO 2 R, C(CH3) :C C02R A NH 2 R -?- - RN(CH 3 CO CH CO 2 R C(CH3) :C C02R By using compounds of the type NH 2 R and acetophenone acetoacetic ester C 6 H 5 CO CH 2.
SALICYLIC ACID (ortho-hydroxybenzoic acid), an aromatic acid, C 6 H 4 (OH)(CO 2 H), found in the free state in the buds of Spiraea Ulmaria and, as its methyl ester, in gaultheria oil and in the essential oil of Andromeda Leschenaultii.
Reimer, Ber., 1876, 9, p. 1285); and by the action of sodium on a mixture of phenol and chlorcarbonic ester (T.
Methyl Salicylate, C,H 4 (OH) CO 2 CH 31 found in oil of wintergreen, in the oil of Viola tricolor and in the root of varieties of Polygala, is a pleasant-smelling liquid which boils at 222° C. On passing dry ammonia into the boiling ester, it gives salicylamide and dimethylamine.
Blue Sark or blue shirt) of the old Norsemen, their first landmark on their way from Iceland to the ester Bygd, the present Julianehaab district, on the south-west coast of Greenland.
Paal has also obtained pyrrol derivatives by condensing acetophenone-acetoacetic-ester with substances of the type NH2R.
Amino derivatives similarly result from thio-ureas and a-haloid ketones; the oxy derivatives from a-sulphocyanoketones by the action of caustic alkali; and the carboxylic acids from chloro-aceto-acetic ester, &c. and thioamides.
Darzens (Comptes Rendus, 1904, 139, p. 1214) prepares esters of disubstituted glycidic acids, by condensing the corresponding ketone with monochloracetic ester, in the presence of sodium ethylate.
Its ethyl ester reacts with hydrazine to form hippuryl hydrazine, C,H 5 CO NH CH 2 CO NH NH 2, which was used by Curtius for the preparation of azoimide.
The latter reacts with chlorine to give silicon nonyl-chloride Si(C2H5)3 C2H4C1, which condenses with potassium acetate to give the acetic ester of silicon nonyl alcohol from which the alcohol (a camphor-smelling liquid) may be obtained by hydrolysis.
Triethyl silicol, (C2H5),Si OH, is a true alcohol, obtained by condensing zinc ethyl with silicic ester, the resulting substance of composition, (C2H5)3 SiOC2H51 with acetyl chloride yielding a chloro-compound (C2H5)3SiC1, which with aqueous ammonia yields the alcohol.
By heating with phosphorus pentachloride an alkyl group is eliminated and a chlorcarbonic ester formed.
Dimethylcarbonate, CO(OCH 3) 2, is a colourless liquid, which boils at 90.6° C., and is prepared by heating the methyl ester of chlorcarbonic acid with lead oxide.
Chlorcarbonic ester, Cl CO.
Rhamnose or isodulcite, a component of certain glucosides, fucose, found combined in seaweeds and chinovose, present as its ethyl ester, chinovite, in varieties of quina-bark, are methyl pentoses.
When heated to about 200° it yields a brown amorphous substance, named caramel, used in colouring liquors, &c. Concentrated sulphuric acid gives a black carbonaceous mass; boiling nitric acid oxidizes it to d-saccharic, tartaric and oxalic acids; and when heated to 160° with acetic anhydride an octa-acetyl ester is produced.
Propylene is liberated during the reaction, and the phosphoric acid ester of meta-cresol which is formed is then fused with potash.
Curtius, Ber., 18 94, 2 7, p. 779; 1896, 29, p. 1166), N2H4ï¿½H20 HONO Rï¿½Cooh-Rï¿½COOR' -- Rï¿½CONHï¿½NH 2 - > acid ester hydrazide C 2 H50H HCI R.
Of foremost importance are the reactions termed the malonic acid and the aceto-acetic ester syntheses; these are discussed under their own headings.
It is therefore apparent that a mixed salt and ester, for example KO 2 Cï¿½CH 2 ï¿½CH 2 ï¿½CO 2 C 2 H 5, would give only two ions, viz.
If a solution of potassium acetate be electrolysed the products are ethane, carbon dioxide, potash and hydrogen; in a similar manner, normal potassium succinate gives ethylene, carbon dioxide, potash and hydrogen; these reactions may be represented: CH 3 ï¿½CO 2;K CH 3 CO 2 K' CH 2 ï¿½CO 2 1K CH 2 CO 2 K' --> I + + I I -i iI + CH 3 ï¿½CO 21 K CH 3 CO 2 K' CH 2 ï¿½CO 2 iK CH 2 CO 2 K' By electrolysing a solution of potassium ethyl succinate, KO 2 Cï¿½(CH 2) 2 CO 2 C 2 H 5, the KO 2 Cï¿½ groups are split off and the two residues ï¿½(CH 2) 2 CO 2 C 2 H 5 combine to form the ester (CH2)4(C02C2H5)2.
In the same way, by electrolysing a mixture of a metallic salt and an ester, other nuclei may be condensed; thus potassium acetate and potassium ethyl succinate yield CH 3 * CH2 ï¿½ CH2 ï¿½ C02 C2H5.
Its ethyl ester, known as oxamaethane, crystallizes in rhombic plates which melt at 114-115° C. Phosphorus pentachloride converts it into cyan-carbonic ester, the ethyl oxamine chloride first formed being unstable: ROOC CONH2 -R000 C(C1 2) NH 2 --)CN COOR.
It is manufactured by distilling wood in iron retorts at about 50o C., when an aqueous distillate, containing methyl alcohol, acetone, acetic acid and methyl acetic ester, is obtained.
To obtain it perfectly pure the crude alcohol is combined with oxalic, benzoic or acetic acid, and the resulting ester separated, purified, and finally decomposed with potash.
After his removal to the Piombi at Venice in February 1821, he composed several Cantiche and the tragedies Ester d'Engaddi and Iginia d'Asti.
After his release in 1830 he commenced the publication of his prison compositions, of which the Ester was played at Turin in 1831, but immediately suppressed.
In this method of preparation it is found that the secondary alcohols decompose more readily that the primary alcohols of the series, and when sulphuric acid is used, two phases are present in the reaction, the first being the building up of an intermediate sulphuric acid ester, which then decomposes into sulphuric acid and hydrocarbon: C2H 5 OH->C 2 H 5 HSO 4 ->C 2 H 4 +-H 2 SO 4.
Chemically it is the methyl ester of arecaidine.
CINNAMIC ACID, or Phenylacrylic Acid, C9H80 2 or C 6 H 5 CH: CH COOH, an acid found in the form of its benzyl ester in Peru and Tolu balsams, in storax and in some gumbenzoins.
It is detected by heating with ordinary alcohol and sulphuric acid, which gives rise to acetic ester or ethyl acetate, recognized by its" fragrant odour; or by heating with arsenious oxide, which forms the pungent and poisonous cacodyl oxide.
In this reaction a glycerol ester is formed as an intermediate product, and undergoes decomposition by the water which is also produced at the same time.
ANTIPYRINE (phenyldimethyl pyrazolone) (C11H12N20), is prepared by the condensation of phenylhydrazine with acetoacetic ester, the resulting phenyl methyl pyrazolone being heated with methyl iodide and methyl alcohol to loo-110° C.: CH 0=N CH3 C-N CH3 >N C6H5 - II >N C6H6 CH 2 -CO HC-CO Phenyl methyl pyrazolone Antipyrine On the large scale phenylhydrazine is dissolved in dilute sulphuric acid, the solution warmed to about 40° C. and the aceto-acetic ester added.
Methacrylic acid was first obtained in the form of its ethyl ester by E.