None
Butyl alcohol. Tetryl alcohol C4H9OH. All the four possible bodies corresponding to this formula are known. 1. Normal butyl alcohol: bulanol ; propyl carlinol CH3-CH2-CH2-CH2OH ; b.p. 115°, Lieben and Rossi (Compt. rend. 68, 1562) 117-2° (Briihl, Annalen, 203, 16) ; sp.gr. 0°= 0-8233, 20° = 0-8109, 40° = 0-7994, 98-7° = 0-7738, 20°/4° = 0-8099 (B.); na= 1-39909, mol. refraction =35-45 (B.). Occurs in the heavy oil of Cognac brandy to the extent of 49 p.c. Is not formed in the fermentation of sugar produced by elliptical yeast (Claudon and Morin, Chem. Soc. Trans. 1887, ii. 714). Is produced by the action of sodium amalgam upon butyryl chloride and butyric acid (Saytzeff, Zeitsch. Chem. 1870, 108; Linnemann, Annalen, 161, 178). Also by the fermentation of glycerol b^y Bacillus butylicus and certain other bacteria in presence of calcium carbonate and various foodstuffs, e.g. ammonium tartrate ; the yield amounts to | 9 p.c. of the glycerol used. Butyric acid and a j little ethyl alcohol are also formed (Fitz, Ber. 9, ! 1348 ; Vigna, Ber. 16, 1348). Is also produced 1 by the action of nascent hydrogen (iron and acetic acid) upon crotonaldehyde and trichloro- butyraldehyde (Lieben and Zeisel, Monatsh. 1, 825, 842). Beyerinck has shown that the Bacillus butylicus of Fitz (Ber. 1882, 867) is in reality the butyric ferment. The true butylic ferment, Granulobacter butylicum, has been isolated in a pure condition, and an account of the whole fermentation process is given ( J. Soc. Chem. Ind. 1894, 167 ; ibid. 969). (See also Emmerling, Ber. 1896, 2726; 1897, 451; Buchner and Meisenheimer, Ber. 1908, 1410.) Properties. — Colourless liquid, soluble in 12 parts of water, from which solution it can be separated by means of calcium chloride. Soluble in concentrated hydrochloric acid ; is readily oxidised to butyric acid. Fused zinc chloride abstracts water, and yields £-butylene and smaller amounts of normal butylene (Le Bel and Greene, Amer. Chem. J. 2, 24). Bromine acting on w-butyl alcohol yields, with some difficulty, mono-brombutaldehyde, i b.p. 235° (fetard, Compt. rend. 114, 753). The j action of aluminium amalgam on the butyl i alcohols, producing liquid aluminium alkoxides, i has been studied by Tistshenko (Chem. Soc. Abstr. 1899, i. 408). 2. Iso-butyl alcohol, isoprol carbinol- I a-%<frozy£-me%Z#ro^ane(CH3)2CH-CH2OH,b.p. ! 108-4° (Linnemann, Annalen, 160, 238) ; sp.gr. i 0-7265 at 106-6°/4° (Schiff, Annalen, 220, 102), 0-8168 at 0° (L.), 0-8069 at 15°/15°, 0-8008 at I 25°/25° Perkin (Chem. Soc. Trans. 1884, 468) ; pp. ! heat=0-686 ; molecular rotation=4-936 at 17-7° (P.); molecular refraction = 35-41 ; /j. = 1-4007. Sp.gr. of aqueous solutions (Duclaux, Ann. hi ; Chim. Phys. [5] 13, 91) : Percentage of alco- \9 _ hoi (by vol.) f2'5 0-^30 0-9915 0-9875 584 BUTYL OR TETRYL. Occurs in fusel oil from potatoes and beet (Wurtz, Ann. Chim. Phys. [3] 42, 129), and combined with angelic and isobutyric acids in Roman oil of chamomile (Kobig, Annalen, 195, 96). Preparation.— By the action of sodium amalgam and water upon j8-chlorisobutyl alcohol, which results from the action of hypochlorous acid upon isobutylene (Butlerow, Annalen, 144, 24). Is formed in small quantity by the action of elliptical yeast upon sugar or glycerol (Claudon and Morin, Chem. Soc. Trans. 1887, ii. 714). By the reduction of isobutyric aldehyde with sodium amalgam (Linnemann and Zotta, Annalen, 162, 11). Properties. — Colourless liquid, soluble in 10-5 parts of water, from which calcium chloride causes it to separate. Smells like fusel oil. is oxidised by chromic acid into isobutyric acid, acetic acid, carbon dioxide, acetone, and other products (Kramer, Ber. 7, 252 ; Schmitt, ibid. 8, 1361). Zinc-dust yields water and iso- butylene (Jahn, ibid. 13, 989). Treated with iodine and aluminium, alumi- nium triisobutoxide A1(C4H90)3 is formed. It is a liquid which may be distilled in vacua (Glad- stone and Tribe, Chem. Soc. Trans. 1881, 6). /sobutyl alcohol may be catalytically oxidised to isobutyl aldehyde. The vapour of the alcohol mixed with air, is passed over warm freshly reduced copper spirals and the products collected. A yield of 50 p.c. is obtainable (E. Orlow, J. Soc. Chem. Ind. 1908, 957). When chlorine is passed into dry isobutyl alcohol, and the solution subsequently heated gently, the product can be separated into two fractions, boiling at 80°-100° and 170°-250°. The lower fraction consists of chlorisobutalde- hyde, boiling at 90°-91°; sp.gr. 1-186, 15°/4°. It combines with sodium hydrogen sulphite, and when oxidised with alkaline permanganate yields acetone and hydroxyisobutyric acid C(CH3)2OH' CO OH, melting at 78°. A termolecular polyme- ride C,2H21C1303, which melts at 107°, is obtained by shaking with strong sulphuric acid (A. Brochet, Compt. rend. 114, 1538). If the alcohol is kept cold, the chief product is dichlor- isobutyl oxide C(CH3)2C1-CHC1-0-CH2CH(CH3)2 boiling at 192-5°/760, and of sp.gr. 1-031, 15°/4°. Water is without action on this product at low temperatures, but at 100° produces hydrogen chloride and a-chlorisobutaldehyde and diiso- butylmonochlorisobutyralC(CH3)2Cl-CH(OC4H9) boiling at 218°, and of sp.gr. 0-9355, 15°/4° (A. Brochet, Compt. rend. 118, 1280 ; v. also Brochet, BuU. Soc. chim. 1896, 16 ; ibid. 20). When chlorine is led into hot isobutyl alco- hol, chlorisobutyricisobutyl ester, a£-dichloriso- ! butyric acid, isobutyl ester, mono- and dichlor- | isobutyric aldehyde, isobutyric acid, oxyiso- i butyric acid, crotonic acid CO.C02, and methyl • chloride are produced. Treating aqueous iso- butyl alcohol with chlorine water produces isobutyric acid, and a-chlorisobutyric acid isobutyl ester. Chlorine acting on cold dry isobutyl alcohol in the light produces 1 : 2- dichlorisobutyl ester (Brochet, Ann. Chim. Phys. [7] 10, 363). /sobutyl alcohol, when acted on by bromine, ! readily yields isobutyl bromide, mixed with j isobutyl isobutyrate, and bronusobutaldehyde (Etard, Compt. rend. 114, 753). (For combinations and derivatives of isobutyl alcohol, v. Gladstone and Tribe, Chem. Soc. Trans. 1881, 6 ; Pierre and Puchot, Annalen, 163, 274; and Heindl, Monatsh. 2, 208.) ^.Secondary butyl alcohol, 2-hydroxybu- tane, methyl ethyl carbinol, butylene hydrate. b'P' "° at 738'8 mm' Annalen, 150, 114) ; sp.gr. 0-827 at 0°, 0-810 at 22° (L.). Formed by the action of water upon the compound of zinc -ethyl and aldehyde : CH3CH(C2H5)0-Zn(C2H5) thus: CH3CH(C2H5)0-ZnC2H5+H20 =C4H9OH+ZnO+C2H6 (Wagner, Annalen, 181, 261). Also by acting upon secondary butyl iodide with silver acetate and saponifying the resulting acetate by means of potash. Normal butyl alcohol may be changed into the secondary alcohol ; the normal iodide is heated with potash, and the normal butylene so obtained on treatment with hydri- odic acid yields secondary butyl iodide (Saytzeff, Zeitsch. anal. Chem. 1870, 327). It may also be prepared from the normal isomeride by treating w-butylamine with nitrous acid (Meyer, Ber. 10, 130; Kanonnikoff and Saytzeff, Chem. Soc. Trans. 1875, 626). Properties. — Liquid, with strong odour ; upon oxidation yields a ketone C2H5-CO-CH3 (b.p. 80°), and acetic acid (Kanonnikoff and Saytzeff, Chem. Soc. Trans. 1875, 626). Heated with a trace of hydrochloric, hydrobromic, or hydri- odic acid, in a sealed tube, to 240°, yields C4H8 (pseudo-butylene). It has been separated into its optical antipodes by R. Meth (Ber. 1907, 695) ; the alcohol has [a] , 0-32°. 4. Tertiary butyl alcohol, trimethyl carbinol (CH3)3C-OH. A solid; m.p. 25-45° (De Forcrand, Compt. rend. 136, 1034) ; b.p. 82-94° (corr.) (Linnemann, Annalen, 162, 26); 81-5°-82° (Perkin, Chem. Soc. Trans. 1884, 468). Sp.gr. 0-7792 at 37° (L.) ; 0-7788 at 30° (Butlerow, Annalen, 162, 229) ; 0-7864 at 20°/4°, 0-7802 at 26°/4° (Briihl, Annalen, 203, 17); 0-7836 at 25°/25°, 0-7761 at 35°/35° ; molecular rota- tion at 24-3° = 5-122 (P.); ^ =1-3924; mole- cular refraction = 35-53 ; crit. temp. = 234-9° (Pawlewski, Ber. 16, 2634). Formed from isobutyl iodide by treatment with acetic acid and silver oxide (Linnemann ; Butlerow, Annalen, 168, 143) ; also from iso- butylamine by treatment with nitrous acid, and from isobutyl carbimide CO-N-C4H4, by action of potash (Linnemann, Annalen, 162, 12). Can be prepared by allowing 20 grams of tertiary butyl iodide and 50 grams of water to stand in contact for two or three days (Dobbin, Chem. Soc. Trans. 1880, 238). /sobutyl alcohol heated with excess of hydro- chloric acid yields a mixture of secondary and tertiary butyl chlorides, and when heated with six volumes of water only the latter is decom- posed, yielding the alcohol and hydrochloric acid (Freund, J. Pharm. Chim. [2] 12, 25). Properties. — Forms rhombic plates or prisms. Unites with water to form a liquid hydrate 2C4H10O,H20 (b.p. 80°; sp.gr. 0-8276 at 0° (Butlerow, Annalen, 162, 229). On oxidation BUTYL OR TETRYL. 585 yields acetone, carbon dioxide, acetic acid, and a small quantity of isobutyric acid (Butlerow, Zeitsch. Chom. J871, 485). The existence of the hydrate C4H10O, 2IL <>, in. p. 0°, is confirmed by cry<>s< c.pie, density and viscosity determinations (Paterno and Midi, Atti. R. Accad. Lincei. 1907 (v.)» 16, ii. 153). In sunlight it combines with chlorine, form- ing tertiary butyl chloride and other substances (D'Otreppe, J. 1881, 512). Trimethyl carbinol explodes feebly when treated with bromine, yielding isobutylene bromide. C(CH3)2Br-CH2Br boiling at 148° (Etard, Compt. rend. 114, 753). Tertiary butyl alcohol has a slightly narcotic action when taken internally, and is found hi the urine in combination with glycuronic acid (Thierfelder and v. Mering, Chem. Soc. Abstr. 1885, i. 1002). Xitrohydroxybutanes may be obtained quanti- tatively as follows: By the action of nitromethane on formaldehyde, in presence of a little potassium carbonate, tertiary nitrotrihydroxy butane NO2-(CH2OH)3,a white crystalline solid, melting at 158°-159°, is produced. Nitroethane pro- duces tertiary nitrodihydroxybutaneN02-C(CH3) (CH2OH)2, melting at 139°-140°. Secondary nitropropane yields nitroisobutyl alcohol N02-C(Me)2-CH2OH, melting at 82° (L. Henry, Compt. rend. 1895, 121, 210). Butyl bromides. Tetryl bromides C4H9Br. 1. Normal butyl br'omide, a-bromobutane CH3-CH,-CH2-CH2Br ; b.p, 99-9° (corr.) (Linnemann, Annalen, 161, 193) ; sp.gr. 1-3050 at 0°, 1-2792 at 20°, 1-2571 at 40° (Lieben and Rossi, ibid. 158, 161). Formed from normal butyl alcohol and hydrobromic acid (L. and R.). By the action of bromine, a£-dibrombutane C4H8Br2 (b.p. 166°) is formed (L.). 2. Isobutyl bromide, a-bromo-yS-methyl propane (CH3),CH-CH2Br ; b.p. 92-3° (corr.) (Linnemann, Annalen, 162, 34) ; 91-3° (Perkin, Chem. Soc. Trans. 1884, 459); sp.gr. 1-2038 at 16° (L.), 1-2722 at 15°/15°, 1-2598 at 25°/25° (P.). Molecular rotation =8 -003 at 16-2° (P.). From t'.sobutyl alcohol, bromine, and phosphorus (Wurtz, Annalen, 93, 114). Unites with bromine at 150° to form C4H7Br3 (L.). ^.Tertiary butyl bromide, $-bromo-&-methyl propane (CH3),CBr; b.p. 72° at 761-5 mm.; sp.gr. 1-215 at 20°, 1-2020 at 15°/15°, 1-1892 at 25°/25°; molecular rotation =8 -238 at 17-8° (P.). Formed when isobutyl bromide is heated to 240° (Eltekow, Ber. 8, 1244). Also from trimethyl carbinol and phosphorus pentabromide(Reboul, J. 1881, 409). May also be prepared by leading isobutylene into a solution of hydrobromic acid of sp.gr. 1-7 (Roozeboom, Ber. 14, 2396). Is readily decomposed at 300° into t'sobutylene and hydrobromic acid. Water, in the cold, forms the alcohol. 4. Secondary butyl bromide, 0-brom- bulane CH3-CH2-CHBr-CH, ; b.p. 90°-93° (V. Meyer and Miiller, J. pr. Chem. [2] 46, 183) ; obtained from secondary butyl alcohol by the action of hydrobromic acid, and yields # (7)- dibrombutane by warming with iron and bromine. Butyl chlorides. Tetryl chlorides C4H9C1. 1. Normal butyl chloride, a-c.hlorbiitane ('II;,-' H,-('HVCH2C1; l..|>. 77-!M>° (corr.) ( Liimrmanu, Annalen, 151, ]!)?): jn.gr. 0-!M)74 at 0°, 0-S.S71 ;il L'O0 (Lichen and Rossi, ibid. 158, 161); 0-9071 at 0° (L.), 0-8972 at 14°. Formed by the action of chlorine upon w-butane (Pelouze and Cahours, J. 1863, 524). More easily by the action of hydrochloric acid upon n-butyl alcohol (Lieben and Rossi). 2. Isobutyl chloride, ft-methyl-a-chlorpro- pane (CH3),CH-CH.,C1 ; b.p. 68-5° (Linne- mann, Annalen, 162, 17); 68-5°-69° (Perkin, Chem. Soc. Trans. 1884, 451); sp.gr. 0-8798 at 15° (L.), 0-8953 at 0°, 0-8651 at 27-8°, 0-8281 at 59° (Pierre, Puchot, Annalen, 163, 276), 0-8835 at 15°/15°, 0-8739 at25°/25° (P.). Mole- cular rotation at 21-3°=6-144 (Perkin). Formed by the action of hydrochloric acid or PC13 upon the alcohol (Wurtz, ibid. 93, 113). By the action of chlorine, hexachlorbutane is produced. /sobutyl chloride is also produced, by the interaction of chlorine and isobutane in diffused sunlight (Mabery and Hudson, Amer. Chem. J. 19, 245) ; and also by treating a'sobutylamine cooled to —15° with nitrosyl chloride (Solonina, Chem. Zentr. 1898, ii. 887)". 3. Tertiary butyl chloride, p-methyl-fi- chlorpropane (CH3)3CC1 ; b.p. 51°-52° (Perkin, Chem. Soc. Trans. 1884, 451); sp.gr. 0-8658 at 0° (Puchot), 0-8471 at 15°/15°, 0-8368 at 25°/25°; molecular rotation at 15° = 6-257 (Perkin). Formed (1) by the chlorination of tertiary butane (Butlerow) ; (2) by the action of iodine monochloride upon isobutyl iodide (Linnemann, Annalen, 162, 18) ; (3) by the action of hydro- chloric acid upon tsobutylene at 100° (Zalessky, Ber. 5, 480 ; Le Bel, Bull. Soc. chim. 28, 462) ; (4) by saturating trimethyl carbinol at 0° with HC1 gas (Schramm, Monatsh. 9, 619). Heated with five or six vols. of water to 100°, the alcohol is produced (Butlerow, Annalen, 144, 33). Chlorine in diffused daylight, in the cold, forms C4H,C12 (b.p. 106°-107°), C4H7C13 and C4H5C15, whilst" in direct sunlight C4H4C16 (b.p. in partial vacuum about 115°), and other products are formed (D'Ottreppe, J. 1882, 441). Tertiary butyl chloride is also formed by the action of PC16 on trimethyl carbinol ( Janschenko, Chem. Zentr. 1897, ii. 334). It also results, together with isobutyl chloride from the action of nitrosyl chloride on tertiary butylamine in xylene solution at —15° to —20° (Salonina, ibid. 1898, ii. 888). 4. Secondary butyl chloride, 0-chlorcbu- tane CH3-CH2-CHC1-CH3, is produced by the action of nitrosyl chloride on secondary butyl- amine in xylene solution at —20° (So^onina$ Chem. Zentr. 1898, ii. 888). Butyl cyanates. Only the e'so-cyanates have been described. 1. Isobut'yl isocyanate. Isobutyl carbi- mide (CH3)2CH-CH2-NCO ; b.p. 110° obtained by the distillation of isobutyl iodide with silver cyanate and sand (Brauner, Ber. 12, 1877). 2. Tertiary, butyl isocyanate (CH3)3C-NCO ; b.p. 85-5° (corr.); sp.gr. 0-8676 at 0° ; remains liquid at —25°. Is formed, together with other substances, when silver cyanate acts upon isobutyl iodide (Brauner, Ber. 12, 1874). By the action 58G BUTYL OR TETRYL. of hydrochloric acid, forms tertiary butylamine (CH3)3C-NH2. Potash produces symmetrical diasobutyl urea, melting at 242°. Butyl cyanides. C4H9CN. 1. Normal butyl cyanide, valeronitrile CH3-CH2-CH2-CH2CN ; b.p. 1404° at 739-3 mm. ; sp!gr. 0-8164 at 0° (Lieben and Rossi, Annalen, 158, 171). 2. Isobutyl cyanide (CH3)2-CH-CH,-CN ; b.p. 126°-128° at 714 mm. (Erlenmeyer and Hell, Annalen, 160, 266); 129-3°-129-5° at 764-3 mm. (R.Schiff, Ber. 19,567); sp.gr. 0-8227 at 0°, 0-8069 at 20° (Erlenmeyer and Hell) ; 0-6921 at 129°/40 (S.). Formed by the oxidation of gelatin (Schlieper, Annalen, 59, 15) or casein (Gunckelberger, ibid. 64, 76) with chromic acid ; also by the action of P205 upon ammonium asovalerate (Dumas, Malaguti, and Leblanc, ibid. 64, 334). May be prepared by heating 300 grams asobutyl iodide, 98 grams of potassium cyanide, 98 grams of alcohol, and 25 grams of water for three days on the water-bath (Erlen- meyer and Hell). 3. Tertiary butyl cyanide (CH3)3C-CN; m.p. 15°-16°; b.p. 105°-106°. Formed by mixing 100 parts of tertiary butyl iodide, 110 parts of mercury potassium cyanide Hg(CN)2* 2KCN with 75 parts of dry magnesia, and allow- ing the mixture to remain for two or three days at a temperature not exceeding 5°. The mass is then treated with water, and distilled on the paraffin-bath (Butlerow, Annalen, 170, 154). 4. Secondary butyl cyanide, methylethyl acetonitrile C2H5-CH3-CH-CN ; b.p. 125°; sp.gr. 0-8061 at 0°. Sodium (£ eqv.) is dissolved in acetonitrile in benzene, and ethyl iodide (1 eqv.) added (Hanriot and Bouveault, Bull. Soc. chim. (3), 1, 172). Butyl hydrides. Butanes, tetranes. 1. Normal butane, diethyl, methylpro- pane CH3-CH2-CH2-CH3 ; b.p. 1° (Butlerow, Zeitsch. Chem. 1867, 363); sp.gr. 0-60 at 0° (Ronalds, Chem. Soc. Trans. 1865, 54). Occurs in crude petroleum (Ronalds, Lefebvre, Zeitsch. Chem. 1869, 185). Formed by heat- ing ethyl iodide with zinc to 150° (Frank- land, Annalen, 71, 173; Schoyen, ibid. 130, 233). Also by the action of sodium amalgam upon ethyl iodide (Lowig, J. 1860, 397). A colourless gas, insoluble in water. 1 vol. of alcohol at 14-2° and 744-8 mm. absorbs 18-13 vols. of butane (Frankland). 2. Isobutane, trimethylmethane (CH3)3CH; b.p. —17°. Formed by heating 0-9 part of isobutyl iodide with 2-4 parts of aluminium chloride to 120° (Kohnlein, Ber. 16, 562). Also by the action of zinc and water upon tertiary butyl iodide (Butlerow, Annalen, 144, 10). The gas is readily soluble in alcohol, from which it can be expelled by dilution with water. CH2-CH2 3. Cyclobutane, tetramethylene, | CH2— CH2 has not yet been obtained, but many derivatives have been prepared by Perkin (Chem. Soc. Trans. 1893, 693 ; 1894, 950). Butyl iodides. Tetryl iodides C4H9I. 1. Normal butyl iodide CH3-CH2-CH2-CH2I ; b.p. 129-8° (corr.) (Linnemann, Annalen, 161, 196); 130-4°-131-4° at 745-4 mm. (Bruhl, ibid. 203, 21); sp.gr. 1-643 at 0°, 1-6136 at 20° (Lieben and Rossi, ibid. 158,163), 1-6 166 at 2074° (Bruhl). From n-butyl alcohol and hydriodic acid (Linne- mann, ibid. 161, 196). By the action of iodine trichloride at 250° it yields hexachlorethaiie C..CL (Krafft, Ber. 10, 805). 2. Isobutyl iodide, a-iodo- fi-methylpro- pane (CH3)2-CH-CH2I ; b.p. 120-0° (corr.) (Linnemann, Annalen, 160, 240 ; 192, 69) ; 83°-83-25° at 250 mm. (Perkin, Chem. Soc. Trans. 1884, 451); sp.gr. 1-6401 at 0° (L.), 1-6056 at 20°/4° (Bruhl, Annalen, 203, 21), 1-6138 at 15715°, 1-6007 at 25°/25° (P.). Molecular rotation at 19-4°= 12-199 (P.). From wobutyJ alcohol, phosphorus, and iodine (Wurtz, Annalen, 93, 116). 3. Secondary butyl iodide, p-iodobutane C2H5-CHI-CH3 ; b.p. 117M180 (Luynes, Bull. Soc. chim. 2, 3); 119°-120° (Lieben, Annalen, 150, 96); sp.gr. 1-6263 at 0°/0°, 1-5952 at 2070°, 1-5787 at 307'0° (Lieben). Formed by distilling erythritol with hydriodic acid (Luynes) or from ^-butylene and hydriodic acid (Wurtz, Annalen, 152, 23). (See also Clarke, Chem. Zentr. 1908, ii. 1015.) 4. Tertiary butyliodide, fi-methyl-fi-iodo- propane (CH3)3CI ; b.p. 98°-99° (with decom.) (Butlerow) ; 100-3° (Puchot, Ann. Chim. Phys. [5] 28, 546); sp.gr. 1-571 at 0°, 1-479 at 53° (P.). From tertiary butyl alcohol and hydriodic acid or «sobutylene and hydriodic acid (Butlerow, Annalen, 144, 5, 22) ; is easily decomposed (by silver oxide, potash, or by heating with zinc and water), into hydriodic acid and ^obutylene (Butlerow, Zeitsch. Chem. 1867, 362). Is also decomposed by water in the cold, yielding hydriodic acid and tertiary butyl alcohol. On heating with sodium, yields a mixture of hydro- gen, tsobutylene, and tmsobutylene (C12H24) (Dobbin, Chem. Soc, Trans. 1880, 236). Butyl mercaptans C4H9-SH. 1. Normal butyl mercaptan CH3-CH2-CH2-CH2-SH; b.p. 97°-98° ; sp.gr. 0-858 at 0° (Saytzeff and Grabowsky, Annalen, 171, 251 ; 175, 351). 2. Isobutyl mercaptan (CH3)2CH-CH2SH ; b.p. 88°; sp.gr. 0-848 at ll-5°(Humann, Annalen, 95, 256), 0-83573 at 20°/4° (Nasini, Ber. 15, 2882). 3. Secondary butyl mercaptan C2H6-CH(SH)CH3 ; b.p. 84°-85° ; sp.gr. 0-8299 at 17°. The mercury compound (C4H9S)2Hg melts at 189° (Reymann, Ber. 7, 1287). 4. Tertiary butyl mercaptan (CH,)?OSH is prepared from tertiary butyl iodide, zinc sulphide, and alcohol (Dobbin, Chem. Soc. Trans. 1890, 641). It boils at 65°-67°, and solidifies in a freezing mixture. Butyl nitrates. 1. Normal butyl nitrate CH3-CH2-CH2-CH2-0-N02; boils at 136° ; sp.gr. 1-048 at 0° (Bertoni, Gazz. chim. ital. 20, 374). 2. Isobutyl n^ra«e(CH3)2CH-CH2-0-N02 b.p. 123° ; sp.gr. 1-0384 at 0°, molecular rotation at 8-9°=5-18 (P.) ; molecular refraction =46 -72 (P.); b.p. 123-5°-124-5° (Perkin, Chem. Soc. Trans. BUTYL OR TETRYL. 587 •••S4). sp.gr. 1-0334 at 4°/4°, 1-02G4 10°/10°,. 1-0124 25°/26y (P.). From silver nitrate, urea, ; and zsobutyl iodide (Wurtz, Annalen, 93, 120 ; \ Chapman and Smith, Zeitsch. Ohem. 1869, 433). 3. Secondary butyl nitrate boils at 124°; sp.gr. 1-0382 atOb (Bertoni, Gaz/. chim. ital. 20, ! 375). Butyl nitrites, nitrobutanes C4H9N(). 1. Isobutyl nitrite (CH3)2CH-CH2-N02 ; b.p. 67°; sp.gr. 0-89445 at 0° (Chapman and Smith, Zeitsch. Chem. 1869, 433), 0-8878 at 4°/4°, 0-8806 at 10°/10°, 0-8752 at 15°/15°, 0-8702 at 20°/20°, 0-8652 at 25°/25°; molecular rotation at 8-2°=5-51 ; molecular refraction =43-9 (Perkin, ( 'liL-m. Soc. Trans. 1889, 686 and 757). Prepared by mixing isobutyl alcohol and sulphuric acid, and gradually pouring the cooled mixture, into an aqueous solution of sodium nitrite (1 : 3) ; the upper layer, consisting of tsobutyl nitrite, is decanted, washed with potassium carbonate solution, and dried. It is a pale-yellow liquid, is apt to become acid by keeping, when rapid decomposition sets in. Taken medi- cinally, lowers the blood pressure and produces respiratory paralysis (Dunstan and Woollev, Pharm. J. [3] 19, 487). 2. Tertiary butyl nitrite (CH3)3C-N02 ; b.p. 63°; sp.gr. 0-8914 at 0° (Bertoni, Gazz. chim. ital. 15, 351) ; 67°-68° (Tscherniak, Annalen, 180, 155). From the alcohol and glyceryl nitrite (B.) ; also from the iodide and silver nitrite (T.). A ^yellow, mobile liquid ; soluble in alcohol, ether, and chloroform ; sparingly soluble in water. Aromatic nitrobutyl derivatives. The butyl derivatives of many aromatic nitrohydrocarbons have a musk-like odour, and are sold as ' artificial musk.' Musk Baur, tri- nitro metabntyl toluene C6H(CH3)(NO.,)3C(CH3)3, is formed by nitrating meta butyl toluene with fuming nitric and fuming sulphuric acids. Butyl toluene is formed by Friedel and Craft's method, as described below, by the action of tertiary but}7! bromide on toluene in the presence of alu- minium chloride. Butyl benzene, ethyl benzene, and xylene are formed at the same time. An unsym metrical butyl cresol is formed by adding butyl alcohol and zinc chloride to meta-cresol. When etherified and nitrated, possesses the odour of civet (A. Baur, J. Soc. Chem. Ind. 1892, 307 ; Dingl. poly. J. 273, 522 ; J. Soc. Chem. Ind. 1894, 1218). Butyl xylene may be prepared by passing a current of j'sobutylene gas through a mixture of 5 kilos. ?tt-xylene, 50 grams *sobutyl chloride, and 200 grams aluminium chloride at 10°. The product is washed with water, and the fraction of the oil boiling at 200°-302° collected. Gaseous hydrochloric and hydrobromic acids may be employed to start the reaction (Act. Gesell. fiir Anilin-Fabriken, Fr. Pat. 372603). Butyl ethers (C4H9),0. 1. Normal butyl' ether; b.p. 140-5° at 741-5 mm. (Lieben and Rossi, Annalen, 165, 110) ; sp.gr. 0-784 at 0°, 0-7685 at 20° (L. and R.), 0-7865 at 0° (Douiner, Annalen, 243, 8). By the action of the sodium derivatives of the alcohol upon ?*-butyl bromide (Reboul, Compt. rend. 108, 39). 2. Isobutyl ether [(CH3)2CH-CH2]20 ; b.p. 122°-122-5° (Reboul, Compt. rend. 108, 162); sp.gr. 0-7616 at 15° (R. ). From wobutyl bromide and sodium i-sobutylate (R.). The action of tsobutyl iodide upon potassium zsobutylate — which, according to Wurtz, yields this ether — really gives a mixture of dw'sobutylene and iso- butyl alcohol (Reboul). 3. Secondary butyl ether [C2H5-CH(CH3)]20; b.p. 120°-121° ; sp.gr. 0-756 at 21° (Kessel, Anna- len, 175, 50). From ethylidene chlorhydrin,and zinc ethyl (K.). Formed in mere traces only by the action of secondary butyl bromide upon the sodium derivative of the secondary alcohol (Reboul, Compt. rend. 108, 162). Reboul ob- tained also the following mixed ethers : — Secondary butyl isobutyl ether; b.p. 121°- 122°; sp.gr. 0-7652 at 21°; Normal butyl isobutyl ether; b.p. 131-5°; sp.gr. 0-763 at 15*5; Normal butyl secondary butyl ether ; b.p. 131° ; sp.gr. 0-7687 at 15° ; Normal butyl tertiary butyl ether ; b.p. 124°; but could not obtain the secondary, tertiary, and the ditertiary ethers (Bull. Soc. chim. [3] 2, 25). Butyl sulphides. 1. Normal butyl sulphide [CH3(CH2)3]2S ; ' b.p. 182°; sp.gr. 0-8523 at 0° (Saytzeff, Annalen, ! 171, 253). From butyl iodide and potassium sulphide. Fuming nitric acid yields the sul- phone (C4H9)2S02 (m.p. 43-5°') (Grabowsky, ; Annalen, 175, 348). Nitric acid of sp.gr. 1-3 converts it into the oxide (C4H9)2SO, melting at 32°. 2. Isobutyl sulphide [(CH3)2CH-CH9].,S ; b.p. 172°-173° at 747 mm. (Grabowsky and Sayt- I zeff, Annalen, 171, 254), 170-5° at 752 mm. ' (Beckmann, J. pr. Chem. [2] 17, 445) ; sp.gr. 0-8363 at 10° (B.). Isobutyl disulphide (C4H9).2S2 ; b.p. 220° (Spring and Legros, Ber. 15, 1940). 3. Secondary butyl sulphide (CH3-CH-C2H5)2S ; b.p. 165°; sp.gr. 0-8317 at 23° (Reymann, Ber. 7, 1288). Butyl thiocarbimides. Butyl mustard oils ; tsothiocyanates. 1. Normal butyl thiocarbimide (C4H9)NCS ; b.p. 167° (Hofmann, Ber. 7, 512). From n-butylamine, carbon disulphide, and alcohol (H.). 2. Isobutyl thiocarbimide (CH3)2CH-CH2-NCS ; b.p. 162°; sp.gr. 0-9638 at 14° (Hofmann, Ber. 7, 511). 3. Secondary butyl thiocarbimide C2H6-CH(CH3)NCS ; I b.p. 159-5°; sp.gr. 0-944 at 12°. Occurs in the , ethereal oil from spoon wort (Cochlearia offici- nalis) (Hofmann, Ber. 2, 102 ; 7, 512). 4. Tertiary butyl thiocarbimide (CH3)3C-NCS ; m.p. 10-5°; b.p. 140° at 770-3 mm.; sp.gr. 0-9187 ; at 10°, 0-9003 at 34° (Rudnew, Bull. Soc. chim. I 1880, 300). Has a pleasant aromatic odour. BUTYLAMINES. 1. Monobutylamines. (a) Normal butylamine, aminobutane CH,-CH.,-CHa-CH2-NH2 ; 588 BUTYL OR TETRYL. b.p. 75-5° at 740 mm. (Lieben and Rossi, Annalen, 158, 172); sp.gr. 0-7553 at 0°, 0-7333 at 26° (L. and R.), 0-7401 at 20°(Linnemann and Zotta, Annalen, 1 1)2, 3). Formed* by the action of potassium hy- droxide upon butyl cyanate (Lieben and Rossi) ; also from propyl cyanide by zinc and sulphuric acid (Linnemann and Zotta, Annalen, 162, 3), or from nitrobutane by action of tin and hydrochloric acid (Ziiblin, Ber. 10, 2083). Is miscible with water ; reduces copper, silver, and mercury solutions in presence of alkalis. The chloride forms a yellow crystalline compound with PtCl4, which is almost insoluble in cold water. (b) Isobutylamine, a-amino-p-methylpro- pane (CH3)2CH-CH2-NH2 ; b.p. 68° (Schiff, Ber. 19, 565), 68°-69° (Perkin, Chem. Soc. Trans. 55, 694); sp.gr. 0-7357 at 55° (Linnemann, Annalen, 162, 23), 0-7464 at 4°/4°, 0-7408 at 10°/10°, 0-7363 at 150/150, 0-7283 at 25°/25°; mol. rot. at 15-3° 5-692 ; heat of combustion 726,990. From isobutyl cyanate and potash (Linne- mann, Annalen, 162, 23) ; also from isobutyl iodide and ammonia (Hughes and Romer, Ber. 7, 511); also from isobutyl chloride and ammonia dissolved in water or isobutyl alcohol. All three isobutylamines are produced, the triisobutylamine in largest quantity. The bases can then be separated by means of ethyl oxalate. The product is first separated into two fractions, the one rich in the monoisobutylamine, the other rich in the di- and tri- compounds. To the former water and then ethyl oxalate are added ; the primary base is thus converted into the oxamide C202(NHC4H9)2, which is almost insoluble in boiling water, the secondary amine being changed - into the ethyl oxamate C2H50-C202-N(C4H9)i:. The other fraction (anhydrous) being poured into ethyl oxalate, the primary and secondary bases are converted into oxamates. The tertiary base is distilled off, and the oxamates are saponified by heating with slaked lime. The calcium oxamates can be separated by crystallisation, the diisobutyloxa- mate being the more soluble in alcohol, from which it separates in slender silky needles (Malbot, Compt. rend. 104, 228). Can be produced by heating isobutyl alcohol with ammoniacal zinc chloride to 260° (Merz and Gasiorowski, Ber. 17, 624), or by the action of caustic potash (10 p.c. solution) upon a mix- ture of bromine and isovaleramide (equal mole- cules) at 60° (Hofmann, Ber. 15, 769). Mixed with water, contraction and develop- ment of heat are produced. A mixture of equal volumes of water and isobutylamine has a sp.gr. of 0-9002 at 15°/15°, instead of the calc. density 0-8681 (Perkin, Chem. Soc. Trans. 1889, 696). With absolute alcohol and the amine similar results were obtained, the sp.gr. of a mixture of equal volumes being 0-791 at 15°/15°, instead of 0-7652, the calculated number. (c) Secondary butylamine C2H5-CH(NH2)'CH3; b.p. 63°; sp.gr. 0-718 at 23°(Menschutkin, Chem. Zentr. 1898, i. 702). Formed by the action of potash upon secondary butyl cyanate, or of am- monia upon secondary butyl iodide (Hofmann, Ber. 7, 513). Also by the action of dilute sul- phuric acid upon secondary butyl mustard oil (Reymann, Ber. 7, 1289). By the reduction of methyl ethyl ketoxime by hydrogen and finely divided nickel at 160°-170°, secondary butylamine and di- secondary butylamine are produced. They are liquids, the latter boiling at 132°/758 mm. and forming an oxalate melting at 104° (Mailho, Compt. rend. 1905, 113). Secondary butylamine has been separated into its optical antipodes by Thom6 (Ber. 1903 582); [O]D 7-42° at 20°. (d) Tertiary butylamine (CH3)3C-NH2 ; b.p. 45-2° at 760 mm. (Rudnew, Chem. Soc. Abstr. 1879, 40, 141); 43-8° at 760 mm. ; sp.gr. 0-7137 at 3°, 0-7054 at 8°, 0-6931 at 15° (R.). Formed in small quantity by the action of potash upon isobutyl cyanate (Linnemann, Annalen, 1625 19; Hofmann, Ber. 7, 513). Also as a by-product in preparing trimethyl acetic acid from trimethyl carbinol iodide and mercuric cyanide (Rudnew). 2. Dibutylamines. (a) Di-nortnal butylamine (CH3-CH2-CH2-CH2)2NH ; b.p. 160°. Formed in small quantities by the action of potash upon butyl cyanate (Lieben and Rossi, Annalen, 158, 175) ; also by the action of butyl chloride on ammonia (Berg, Ann. Chim. Phys. [7], 3, 294). Gives [(C4H9)2NH-HCl]2PtCl4; yellow needles, almost insoluble in cold water. (6) Di-iso-butylamine [(CH3)2CH-CH2]2NH ; b.p. 135°-137°; sp.gr. 0-7577 at 4°/4°, 0-7491 at 15°/15°, 0-7425 at 25725° (Perkin, Chem. Soc. Trans. 1889, 697). From isobutyl bromide and alcoholic ammonia at 150° (Ladenburg, Ber. 12, 949) ; also from isobutyl alcohol and ammoniacal zinc chloride at 270° (Merz and Gasiorowski, Ber. 17, 627). The hydrochloride (C4H9)2NH-HC1 forms plates or leaflets easily soluble in alcohol and water, slightly in ether. The platinum com- pound forms dark-red prisms, soluble in water, alcohol, and ether (Malbot, Compt. rend. 104, 366). The nitroso- derivative (C4H9)2N-NO is a disagreeably smeUing oil ; m.p. 0° ; b.p. 213°-216° (with decomposition) ; obtained by the action of potassium nitrite upon the hydro - chloride (Ladenburg, Ber. 12, 949). (c) Di-tertiary butylamine [(CH3)3C]2NH; produced as iodide when tertiary butyl iodide and tertiary butylamine are heated to 50°; at 70° the mixture is decomposed, forming iso- butylene and tertiary butylammonium iodide (Rudnew). The iodide is easily soluble in water or alcohol ; on heating the aqueous solution evolves tertiary butylamine. 3. Tributylamines. (a) Tri-normal butylamine(CiH-9)3~N; b.p. 211°-215°at 740 mm.; sp.gr. 0-791 at 0°, 0-7782 at 20°, 0-7677 at 40°. From butyl cyanate and potash, together with the mono- and di- com- pounds (Lieben and Rossi, Annalen, 165, 115). With butyl iodide forms iodide of tetrabutyl- ammonium N(C4H9)4I, which crystallises in small plates (L. and R.). Also by the action of ammonia on butylchloride ; b.p. 216-5° (Berg. Ann. Chim. Phys. [7] 3, 299). (6) Tri-iao-butylamine (C4H9)3N ; b.p. 177°-180° (Reimer, Ber. 3, 757); 184°-186° (Sachtleben, Ber. 1 1, 733). Sp.gr. 0-785 at 21° (S. ). From diisobutylamine and isobutyl bromide BUTYL OR TETRYL. 580 (R.). From the alcohol and ammoniacal zinc chloride at 270° (Merz and Gasiorowski, Ber. 17, (>27) ; also from tsobutyl iodide and aqueous ammonia at 160° (Malbot, Compt. rend. 105, 574). Is not miscible with water. Forms salts with hydrochloric, nitric, and sulphuric acids, which are extremely soluble and crystallise with difficulty. The platinum double salt forms large ruby-red crystals (Malbot, Compt. rend. 104, 366). Butylenes C4H8. Three isomeric butylenes are possible and all are known. 1. Normal (a)-butylene. Ethyl ethylene CH3-CH2-CH:CH2 ; b.p.-5°. Formation. — From normal butyl iodide and alcoholic potash (Saytzeff, J. pr. Chem. [2] 3, 88 ; Grabowsky and Saytzeff, Annalen, 179, 330). From bromethylene and zinc-ethyl (Wurtz, Annalen, 152, 21). together with butyl alcohol. From normal butylamine and nitrous acid(V. Meyer, Ber. 10, 136). Prepared by digest- ing on the water-bath 100 grams normal butyl iodide, 200 grams potash, and 150 grams alcohol (90 p.c.) (S.). A gas at ordinary tempera- tures, which combines readily with hydriodic acid to form secondary butyl iodide; and with hypochlorous acid to form chloromethylethyl carbinol CH3-CH2-CH(OH)-CH2C1. 2. fi-Butylene. Symmetrical dimethylethyl- ene CH3-CH : CH-CH3 ; b.p. 1° at 741-4 mm. (Lieben, Annalen, 150, 108); sp.gr. 0-635 at —13-5 (Puchot, Bull. Soc. chim. 30, 188). Formed by the action of potash upon secondary butyl iodide (Luynes, Annalen, 129, 200; Lieben, ibid. 150, 108). Together with i'sobutylene by dropping iso- or normal butyl alcohol upon strongly heated zinc chloride (Nevole, Bull. Soc. chim. 24, 122 ; Le Bel and Greene, Amer. Chem. J. 2, 23). From trithio- aldehyde (C2H4S)3 and copper (Eltekow, Ber. 10, 1904). By heating a mixture of methyl iodide and allyl iodide with sodium (Wurtz, Annalen, 144, 235). Preparation. — /sobutyl alcohol is allowed to drop upon heated zinc chloride, and the evolved pis is led into sulphuric acid diluted with half its volume of water ; this retains the isobutylene. The unabsorbed gas is led into bromine, and is again liberated by action of sodium (Le Bel and i.nme, Bull. Soc. chim. 29, 306). Two stereo- i-omerie modifications are known (Wislicenus, Chem. Zentr. 1897, ii. 267). /3- Butylene combines with bromine to form a dibromide boiling at 156°-158°. This compound, by the action of potash, forms mono-bromo- pseudo-butylene CH3-CBr:CH-CH8; b.p. 87°-88° (Holz, Annalen. 250, 230). Chlorine forms a di- chloride ; b.p. 112°-114° (Chechoukow, Bull. Soc. chim. 43, 127). 3. y-Butylene. /sobutylene, unsymmetrical ilinnthi/l rthi/lene (CH3)2C : CH2 ; b.p. —6° (Butlerow, Zeitsch. Chem. 1870, 236). Liquefied by a pressure of 2-2| atmospheres at 1 5°- 18°. Is produced by the dry distillation of fats (Faraday, Phil. Trans. 1825, 440) ; by heating the vapour of fusel oil to redness (Wurtz, Annalen, 104, 249), together with ethylene and ethane : also from light petroleum, ' ligroin ' (b.p. 60°-90°) (Prunier, J. 1873, 347) ; from iso- or tertiary- butyl iodide and alcoholic potash (Butlerow, Annalen, 144, 19) ; by heating trimethyl carbinol and dilute sulphuric acid (1 vol. H2S04 to 2 vols. ; water) (Butlerow) ; from isobutyl alcohol and , zinc chloride, though in very small quantity (Nevole, Bull. Soc. chim. 24, 122). Preparation. — (1) 5 parts of tsobutyl alcohol, 5 parts sulphuric acid, 1 part of water and sand are heated together (Lermontow, Annalen, 196, , 117). (2) Puchot's method (Ann. Chim. Phys. j [5] 28, 508) of heating wobutyl alcohol with a I mixture of sulphuric acid, potassium sulphate, and gypsum, gives a mixture of pseudo- and iso- butylene. (3) A mixture of 2 parts of caustic potash and 3 parts of alcohol (90 p.c.) is slowly added to 2 parts of wobutyl iodide, and j gently warmed (Butlerow, Zeitsch. f. chem. 1870, | 238). Butylene is a gas, with unpleasant smell, slightly soluble in water; combines with hydriodic acid to form tertiary butyl iodide. A mixture of three parts of sulphuric acid and 1 part of water completely absorbs the gas ; on distilling the diluted solution trimethyl carbinol is evolved. It forms a mercury compound C4H8(HgNO3)(Hg2N03) (Deniges, Compt. rend. 126, 1043). Oxidising agents — e.g. potassium permanganate — form carbon dioxide, formic and acetic acids, and oxalic acid (and in the case of chromium trioxide, acetone) (Zeidler, Annalen, 197, 251). By the action of a mixture of 5 parts sulphuric acid and 1 part of water forms dode- cylene (trusobutylene) C12H24; b.p. 177-5°- 178-5°; sp.gr. 0-774 at 0° (Butlerow, Ber. 6, 561). Butylene alcohol v. Butylene glycols. Butylene dibromides. 1. Normal butylene dibromide, afi* \dibrombutane CH3-CH2-CHBr-CH2Br ; b.p. i 165-6°-166° ; sp.gr. 1-876 at 0° (Wurtz, Annalen, ! 152, 23), 1-8503 at 0°, 1-8204 at 20°/0° (Gra- bowsky and Saytzeff, Annalen, 179, 332). Formed from a-butylene and bromine (Wurtz); from normal butyl bromide and bromine at 150° I (Linnemann, Annalen 161, 199). Gives a- I butylene by action of sodium. 2. fi'Butylene dibromide, fiy-dibrom- \ butane CH3-CHBr-CHBr-CH3; b.p. 158°; sp.gr. l-821atO°. Formed from£- butylene and bromine (Wurtz, Annalen, 144, 236), or by heating a- or /3-brombutane with iron and bromine (V. Meyer ; and Muller. J. pr. Chem. [2] 46, 180). Decom- posed by heating to 140° with water and I lead oxide, forming lead bromide and methyl I ethyl ketone (Eltekow, Chem. Soc. Abstr. 1879, !34). 3. Iso-butylene di-bromide, afi-dibrom- \ 0-methyl propane (CH3)2CBr-CH2Br; b.p. 148°- 149° at 737 mm. ; sp.gr. 1-798 at 14° (Linnemann, j Annalen, 162,36). From zso-butylene and bromine i (L. ; also Wurtz, Annalen, 104, 249 ; Hell and Rothberg, Ber. 22, 1737). By heating with water to 150° »sobutyraldehyde and isobutylene glycol are formed. 4. Tetramethylenedibromide, a8-di- brombutane, CH2Br-CH2-CH2-CH,-Br. ; boils at i 188°-190° (Gustavson and Demjanoff, J. pr. Chem. [21 39, 543). (See also Haincourt, Compt. rend. 132, 345.) 5. &0-Dibrombutane CH3-CBr2-CH2-CH3; boils at 144°-145° (Wislicenus and Holz, Anna- ; len, 250, 232). 6. ay-Dibrombutane CH2Br-CH2-CH2Br-CH3; boils at 174°-175° (Perkin" Chem. Soc. Trans. 1894, 963). 590 BUTYL OR TETRYL. Butylene cyanide. Isobutylene dicyanide (dimethyl succi- nonitrile) CN-C(CH3)2-CH,-CN ; b.p. 218°-220°. By treating an aqueous alcoholic solution of potassium cyanide with y-butylene bromide, and allowing the mixture to stand for a fortnight. A colourless oil, moderately soluble in \vater. Heated to 150° with strong hydrochloric acid, it is decomposed into ammonia and dimethylsuc- cinic acid (Hell and Rothberg, Ber. 22, 17,37). Butylene glyeolehlorhydrin, j8-ehloroisobutyl- aleohol (CH3)2-CC1-CH2OH ; b.p. 137. From isobutylene and hypochlorous acid (Butlerow, Annalen, 144, 25). Soluble in large excess of water. See also Michael and Leighton (Ber. 1906, 2157). £-Chloroi$obutyl alcohol is also formed by the union of hydrogen chloride with tsobutylene oxide, which results from the action of dry powdered potassium hydroxide on chloro- trimethyl carbinol. The last may be prepared from magnesium methyl bromide, chloroacetone and ethyl chloroacetate. jS-chloroa'sobutyl alcohol boils at 132°-133°. It forms a nitrate by the action of concentrated sulphuric and nitric acids C(Me)2Cl-CH2N03, and a nitrite C(Me)2Cl-CH2N02 with nitrous acid, which distinguishes it from the isomeric chlorotri- methyl carbinol (L. Henry, Compt. rend. 1906, 142, 493). Butylene diamines. 1. Tetramethylenediamine (putrescine), a5-diaminobutane NH2-CH2-CH2-CH2-CH2-NHo, occurs in urine and faeces in cases of cystinuria, and also arises during the putrefaction of her- rings. It is prepared by reducing an alcoholic solution of dicyanoethylene with sodium (Laden- burg, Ber. 1886, 780 ; Lellmann and Winthaer, Annalen, 228, 229) ; or in a similar manner from succinaldehyde dioxime (Ciamician and Zanetti, Ber. 1889, 22, 1968, 1970). Colourless crystals melting at 27°-28° (C. Z. ) and boiling at 158°-160°. Smells like piperidine. It is strongly basic, readily absorbs CO2, and forms a well-defined dihydrochloride, aurichloride, and platinichloride. The picrolonate is of some physiological import- ance (Otori, Chem. Soc. Abstr. 1905, ii. 126). Willstatter and Heubner have prepared the tetramethyl derivative of tetramethylene dia- mine, and the biquaternary hexamethylammo- nium salt corresponding to it (Ber. 1907, 3871, 3874). The identity of a8-diaminobutane with putrescine rests on the experiments of Udranszky and Baumann (Ber. 1888, 2938). Brieger (Chem. Zentr. 1907, i. 1703) considers the identity not proven, as also do Willstatter and Heubner (I.e.). 2. Dimethylethylenediamine, &y-dia- minobutane CH3-CHNH2-CHNH2-CH3, has been prepared by Angeli (Ber. 1890, 1358). /so-Butylacetie acid v. CAPROIC ACID. Butyl chloral v. CHLORAL. Butyl-lactinie acid v. HYDROX YBUTYRIC ACIDS. Butylene glyeols. 1. Normal-(a)-butylene glycol, aft-di- hydroxybutane CH3-CH2-CHOH-CH2OH ; b.p. 191°-192° at 747-1 mm. ; sp.gr. 1-0189 at 0°/0°, 1-0059 at 17-5/0°. From normal butylene di- bromide (Saytzeff and Grabowsky, Annalen, 179, 332). 2. fi-Butylene glycol, ay-dihydroxybutane CH3-CH(OH)-CH2-CH2OH; b.p. 203-5°-204°(Ke. ! kule', Annalen, 162, 310) ; sp.gr. 1-0259 (Wurtz, ; J. 1873, 474 ; Bull. Soc. chim. 41, 362). Pro- 1 duced in small quantity by the reduction of dilute aqueous solution of aldehyde by sodium-amalgam (K.). Prepared from j8-oxybutyric aldehyde by | reduction with sodium amalgam (W.). 3. Isobutylene glycol, a0-dihydroxu-a- we%£pro^Gwe(CH3)2C(OH)-CH2OH; b.p. 176°- 178° ; sp.gr. 1-0129 at 0°, 1-003 at 20°. Pro- ! duced by the fermentation of sugar in presence of tartaric acid (Henm'nger and Sanson, Compt. rend. 106, 208). Formed by heating isobutylene bromide with potassium carbonate and water (Nevole, Bull. Soc. chim. 27, 63) ; also by oxida- tion of wobutylene by means of potassium per- manganate in neutral aqueous solution (Wanner Ber. 21, 1232). 4. Symmetrical dimethylethylene gly- col, 0y-dihydroxybutane CH3-CHOH-CHOH-CH3- b.p. 183°-184°. Formed by heating for 6 or 7 hours 1 vol. of symmetrical dimethylethylene oxide C4H80 with 3 vols. of water to 100° (Eltekow, Chem. Soc. Abstr. 1883, 566). 5. Tetramethylene glycol, aS-dihydroxy- butane OH-(CH,)4-OH; boils at 203°-205°; sp.gr. 1-0111 (Dekkers, Chem. Soc. Abstr., 1891, 164). 6. A-butylene glycol, differing from the above, boiling at 183°-184°; has also been pre- pared by Wurtz (Ann. Chim. Phys. [3] 55, 452) ; sp.gr. 1-048 at 0°. 7. a-Methyl propanediol OH-CH2-CH(CH3)-CH2OH (Henry, Bull. Soc. chim. [3] 13," 1002 ; Cesaro. Chem. Zentr. 1897, ii. 179). Butylene diiodide, ay-diiodobutane CH3-CHI-CH2-CH2I ; sp.gr. 2-291. From /3-butylene glycol and hydriodic acid (Wurtz, Bull. Soc. chim. 41, 362). Isobutylene dinitrite C4H8(N02)2. By treat- ment of a'sobutylene with concentrated nitric acid (Haitinger, Monatsh. 2, 287). Forms a crystalline mass. Probably the same body was obtained by Beilstein and Kurbatow (Ber. 14, 1621) by treating the petroleum of Tiflis (b.p. 40°-50°) with nitric acid (sp.gr. 1-52). It formed needles which melted at 96°. They were insoluble in water, but soluble in alcohol and ether. Butylene oxides C4H80. 0 1. Isobutylene oxide (CH3)2C CH,; b.p. 51°-52°; sp.gr. 0-8311 atO°. From the chlor- hydrin C4H4C109 and potash (Eltekow, Chem. Soc. Abstr. 1883, 566). 2. s-Dimethylethylene oxide CH3-CH-CH-CH3 ; b.p. 56°-57°; sp.gr. 0-8344 at 0°. Formed from the chlorhydrin (prepared from the symmetrical dimethyethylene and hypochlorous acid) and potash (Eltekow, Chem. Soc. Abstr. 1883, 566). BUTYRALDEHYDE. Butyric aldehydeC^O. This compound exists in two isomeric forms, termed normal and asobutyric aldehyde respec- tively. Normal butyraldehyde CH3-(CH2),-CHO is formed together with acetaldehyde and propal- dehyde by the action of chromic acid upon fibrin, casein, and albumen (Guckelberger, Annalen, 64, 39). It is readily prepared by dis- tilling a mixture of calcium formate (2 mols.) and BUTYRIC ACID. 591 calcium butyrate (1 mol.) in quantities of 50 L'ram.s at a time with twice the weight of iron tilings. The distillate is fractionated, the fraction 70°-110° treated with sodium hydrogen sulphite (bisulphite), then shaken with ether to extract impurities, and finally distilled with excess of soda (Lipp, Annalen, 211, 355 ; Linne- mann, ibid. 161, 186; Kahn, Ber. 1885, 3364). Bodroux has applied Grignard's reagent to a solution of orthoformic and acetaldehyde, thereby obtaining a 75 p.c. yield of butyralde- hyde (Chem. Zentr. 1904, i. 1077). Properties. — Normal butyraldehyde is a liquid which boils at 73°-74° (Lipp, at 73°-77°) and has a sp.gr. 0-8170 at 20°/4° (Briihl, An- nalen, 203, 18). It is soluble in 27 parts of water. With sodium hydrogen sulphite (bisulphite) it unites, yielding a crystalline compound (Justin, Ber. 1884, 2505). When treated with aqueous ammonia at 0°, it yields butyraldehyde-am- monia C4HuNO,3£H2O, which crystallises in acute rhombic tetrahedra and melts at 30°-31° (Guckelberger). If, however, alcoholic ammonia and the aldehyde are allowed to stand for a month, and then heated for a day at 100°, con- densation occurs, and, after removal of ammonia, alcohol and unattacked butyraldehyde by dis- tillation, two bases, tetrabutyraldine and di- butyraldine C8H17NO can be separated by fractional precipitation with platinic chloride. The latter only can be crystallised, and when heated is converted into paraconine C8H15N and Avater (Schiff, Annalen, 157, 352). The trichlo- robutyraldehyde (butylchloral) and its hydrate have been prepared by Pinner (Annalen, 179, 26). /sobutyraldehyde (CH3)2CH-CHO can be pre- pared by the oxidation of tsobutyl alcohol with potassium dichromate and sulphuric acid (Lipp, Annalen, 205, 2 ; Pinner, Ber. 5, 699 ; Fossek, Monatsh. 2, 614 ; 4, 661), or by distilling calcium formate with calcium i^obutyrate (Linnemann and Zotta, Annalen, 162, 7). It dissolves in 9 parts of water at 20°, and is soluble in alcohol and ether. The boiling-point is 63°-64° at 757 mm. (Briihl, Annalen, 203, 18), and the sp.gr. 0-7938 at 20°/4° (Briihl), 0-79722 at 15° (Perkin, Chem. Soc. Trans. 1884, 476). Con- densation compounds have been obtained by Perkin (Chem. Soc. Trans. 1883, 91). BUTYRIC ACID C4H,02. Two isomeric forms of this acid are known, normal butyric and /6-obutyric acid. Normal butyric acid CH3-CH2-CH2-COOH. Occurrence. — In ordinary butter in combina- tion with glycerol to the extent of 2 p.c. ; also in the fruits of Heracleum villosum (Fisch) and of /'< n< idanum sativum (Benth. Cl. Hook, /.) as lu.-xyl butyrate and octyl butyrate respectively. Butyric acid is also found in flesh juice, and is frequently a constituent of decomposing organic matter (v. art. FERMENTATION) (J. 1857, 353, 402, 403,559; 1858,231; 1859,363,364; 1861,454; 1866, 311). The occurrence of butyric acid in sour milk is treated of by Thorpe (Chem. Zentr. 1909, ii. 1774). Preparation. — (1) Butyric acid is a frequent product of the oxidation of organic substances ; ( a<fiiu tilirin. and albumen, for example, yield this acid among other products on oxidation with manganese dioxide and sulphuric acid (Gut-kelberger, Annalen, 64, 68). (2) All amylaceous and saccharine sub- stances which' yield lactic acid as a product of their fermentation can undergo a further fer- mentation to butyric acid, and this fact is made use of for the preparation of the acid. 5 kilos. | of rice or potato starch are boiled with 60 litres of water for some hours, allowed to cool, and the product after 24 hours is treated with 60 grams of malt stirred up with 2 litres of milk, with 1 kilo, of finely divided flesh, and with 2 kilos, of chalk, the chalk being added to neutralise the lactic and butyric acids as rapidly as they are formed, and the whole is allowed to remain with occasional stirring for several weeks at a tempe- rature of 25°-30&. When the evolution of gas has ceased, the product is heated to 80°, filtered, precipitated with sodium carbonate to decompose the calcium salt, again filtered, evaporated to a small bulk, and treated with sulphuric acid. The oily layer of acid so obtained is fractionated to free it from the acetic and caproic acids formed simultaneously, and the fraction 155°- 174° is extracted with water, which dissolves the butyric acid but leaves the caproic acid un- dissolved ; the aqueous extract is then neutral- ised with lime, the solution concentrated, and the salt finally decomposed by hydrochloric acid (Grillone, Annalen, 165, 127). (3) In the presence of a schizomyces — the so-called Bacillus subtilis, which can readily be obtained by stirring hay in Avater, straining the liquor through a sieve, and boiling for 5 minutes — Fitz (Ber. 11, 52) has found that starch readily undergoes fermentation, yielding normal butyrio acid as chief product. Butyric acid has also been obtained by the fermentation of glycerol in 3 p.c. aqueous solution Avith a species of schizomyces (Fitz, Ber. 9, 1348 ; 10, 276), and has been prepared by various synthetical methods (Frankland and Duppa, Annalen, 138, 218; Geuther and Frelich, ibid. 202, 306). (For conditions affecting the production of butyric acid by fermentation, see FERMENTATION.) Properties. — Butyric acid is a colourless, transparent liquid, having an odour resembling that of rancid butter, and a sour burning taste. Cooled to —19° it solidifies, and the crystals melt at about —2°. The acid boils at 161-5° at 760 mm. (Kahlbaum, Ber. 16, 2480) ; at 162-3° (corr.) (Linnemann, Annalen, 160, 228; Zander, ibid, 224, 64); and has a sp.gr. 0-96704 at 15°/15° (Perkin, Chem. Soc. Trans. 1884, 483), 0-9590 at 20°/4° ;/4D, 1-39906 (Scheig, R. 1899, 169). Butyric acid is inflammable and burns Avith a blue flame. Alcohol, wood-spirit, and Avater dissolve it in all proportions, and from the aqueous solution it can be separated by addition of calcium chloride. Prolonged boiling Avith nitric acid converts it into succinic acid. By the action of calcium carbide, dipropyl ketone may be obtained (Haehn, Chem. Zentr. 1906, ii. 17). Salts. — The metallic salts of normal butyric ! acid are generally soluble in Avater, and are crys- i talline. NaB and KB crystallise in indistinct cauliflower-like groups. AgB crystallises in needles or monoclinic prisms, and dissolves in 200 parts of Avater at 14° (Linnemann and Zotta, Annalen, 161, 177) ; 100 parts of water dissolve 0-413 part at 16° (Griinzweig, Annalen, , 162, 203). MgB,,5H,0 crystallises in very soluble scales (Pelouze and Gelis, Annalen, 47 592 BUTYRIC ACID. 249). BaB2,4H20 crystallises in nacreous scales, and dissolves in 2-48 parts of water at 14° (Limiemann and Zotta). CaB2,H20 crystal- lises in rhombic forms; 100 parts of water dissolve 19-4 parts at 0°. (For solubility table, see Hecht, Annalen, 213, 72.) SiB2formsmonoclinic prisms ; 100 parts of water at 20° dissolve 39-2 parts of the salt (Griinzweig). ZnB2,2H20 forms monoclinic prisms ; 100 parts of water at 16° dissolve 10-7 parts of the crystallised salt (Griinzweig). PbB2 is an oil which slowly solidifies (Markownikow, Annalen, 138, 361). CuB2,H20 crystallises in triclinic forms (Alth, Annalen, 91, 176), and CuB2,2H20 crystallises in monoclinic forms (Pelouze and Gelis). Separation from formic, acetic, and propionic acids. — Mach and Portele (Chem. Soc. Abstr. 