T. E. (Thomas Edward) Thorpe.

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I tary rocks and as masses in mineral- veins, and
' has sometimes been observed as a decomposi-
' tion product of granite and other rocks con-
, taining felspar. Possibly the minute amor-
: phous granules of china-clay and some other
i clays may be referable to this species. (See H.
Ries, Clays, their Occurrence, Properties, and
I Uses, 2nd ed., 1908.) L. J. S.

HALOGEN. A term originally applied by
Berzelius to the group of non-oxygenated electro-
i negative radicles^, simple and compound, which
! combine with metals to form salts known as
I haloid salts. Usually restricted to the four
elements Fluorine, Chlorine, Bromine, and
1 Iodine.

I HALOGEN ACETIC ACIDS. Derivatives of
acetic acid in which the hydrogen of the methyl
group is partly or wholly replaced by a halogen.

Chloroacetio Acids.
Monochloroacetic acid CHgClCOOH. Pre-
pared by passing chlorine into acetic acid alone
(Hoffmann, Annalen, 102, 1), or in the presence
of iodine (Miiller, ibid. 133, 156), sulphur (Auger
and Behal, Bull. Soc. chim. [iii.] 2, 145), or red
: phosphorus (Russanow, J. Russ. Phys^. Chem.
j Soc. 23, 222) ; by the action of chlorine on acetyl
I chloride in the presence of iodine ( Jazukomtsch,
! Zeitsch. Chem. 1868, 234) ; by the interaction
I of chlorine, glacial acetic acid, and acetic anhy-
I dride at 100 (Hentschel, Ber. 1884, 17, 1286) ;
I together with acetyl chloride by the action of
chlorine on acetic anhydride at 100 (Gal,
Annalen, 122, 374) ; by the interaction of
ethylene and chlorine peroxide (Fiirst, ibid.
206, 78).

Crystallises in two modifications, o- prisms,
m.p. 61*8 ; fi- plates, m.p. 56-01. By evaporat-
ing an aqueous solution or by melting the solid
substance, the )8- modification is produced ; this
changes to the a- form on the addition of a
crystal of the latter (Pickering, Chem. Soc.
Trans. 1895, 665, 670; c/. Tollens, Ber. 1884,
17, 665; Tanatar, J. Russ. Phys. Chem. Soc.
24, 694); b.p. 185-187, 104-105/20 mm.
(Sudborough and Lloyd, Chem. Soc. Trans.
1899, 476) ; sp.gr. 1-3978 at 64-5 ; hydrates
(Colles, ibid. 1906, 1252); heat of solution



30



HALOGEN ACETIC ACIDS.



(Pickering, I.e. ; Luginiri, Ann. Chim. Pliys. [v.]
17, 251; Tanatar, I.e.); heat of combustion
171-0 Cals. (Berthelot, ibid, [vi.] 28, 567);
electrical conductivity (Kortright, Amer. Chem.
J. 18, 368) ; magnetic rotation (Perkin, Chem.
Sec. Trans. 1896, 1236) ; esterification constant
(Sud borough and Lloyd, I.e. ; .c/. Lichty, Amer.
Chem. J. 1895, 17, 27 ; 1896, 18, 590). Readily
soluble in cold water, but on heating the solution
decomposes into hydrochloric and glycollic acids
(Buchanan, Ber. 1871, 4, 340, 863 ; Thomson,
Annalen, 200, 75 ; Bevan, Proc. Camb. Phil.
Soc. 1906, 13, 269 ; Senter, Chem. Soc. Trans.
1907, 460). Metallic hydroxides of the type
R'OH decompose it, yielding glycollic acid,
whilst those of the type R"(0H)2 yield diglycollic
acid (Schreiber, J. pr. Chem. [ii.] 13, 346). By
heating salts of chloroacetic acid with water in a
sealed tube glycollic acid is produced (Kastle,
Amer. Chem. J. 1892, 14, 586 ; Kastle and Keiser,
ihid. 1893, 15, 471 ; ef. Euler, Ber. 1906, 39,
2726). On distilling the acid in vacuo with
phosphorus pentoxide, the anhydride

(CH2C1C00)20
is produced, whilst by distilling the acid through
a heated tube, carbon monoxide, hydrogen
chloride, s^/m-dichloromethyl ether and trioxy-
methylene are the products (Grassi-Cristaldi,
Gazz. chim. ital. 27, ii. 502). On heating with
4 parts of phosphorus pentachloride, it yields
carbon tetrachloride and other products (Michael,
J. pr. Chem. [ii.] 35, 96) ; with ammonia glycine
is produced. By interaction with sodium
sulphide and sulphur in alkaline solution a
dithioglycoUic acid is produced, which on reduc-
tion, yields thioglycollic acid (Kalle & Co.
D. R. P. 180875; Chem. Soc. Abstr. 1907, i.
1008). By the electrolysis of the potassium
salt acetic acid, carbon dioxide and chlorine are
formed, hydrogen not being evolved until the
potassium salt is completely decomposed
(Lassar Cohn, Annalen, 251, 335 ; cf. Bunge, J.
Russ. Phys. Chem. Soc 24, 690). By heating
the dry silver salt, silver chloride and glycoUide
are produced (Beckurts and Otto, Ber. 1884, 14,
576). The sodium salt or the ethyl ester react
with potassium cyanide to yield the correspond-
ing derivatives of cyanacetic acid (Phelps and
Tillotson, Amer. J. Sci. 1908, [iv.] 26, 267, 275).
For interaction mth tertiary amines to yield
betaiues, v. Reitzenstein, Annalen, 1903, 326,
305 ; with aniline, v. Vallee, Bull. Soc. chim.
1905, [iii.] 33, 966 ; with hydro xylamine, v.
Rivals, Compt. rend. 1896, 122, 1489; with
thiocyanic acid or its salts, v. Nencki, J. pr.
Chem. [ii.] 16, 1 ; Jager, ibid. 17 ; with phenols,
V. Saarbach, ibid. 21, 151 ; with nitrogen sulphide,
V. Francis, Chem. Soc. Trans. 1905, 1839.

Methyl ester. Prepared by passing chlorine
into methyl acetate at 110-120 (Censi, Bull.
Soc. Lid. Mulhouse, 70, 311), and as ethyl ester
{q.v.) ; b.p. 115 (Censi, I.e.), 130 at 740 mm.
(Schreiner, Annalen, 197, 8 ; cf. P. Meyer, Ber.
1875, 8, 1152); sp.gr. 1-2352 at 19-2 (Henry,
J. 1885, 1329).

Ethyl ester. Prepared by the interaction of
chloracetyl chloride and alcohol (Willm, Anna-
len, 102, 109), or by the action of alcohol on
monochloroacetic acid in the presence of sulphuric
acid (Conrad, ibid. 188, 218) ; b.p. 144-5-144-9
at 754-2 mm. : sp.gr. M585 at 2074 (Briihl,
ibid. 203, 209). Condensation products are



formed with ethyl sodiomalonatc (Michael, Ber.
1905, 33, 3217) ; benzylamine (Mason and
Winder, Chem. Soc. Trans. 1894, 628) ; phenyl-
hydrazine (Reissert, Ber. 1895, 28, 1231 ; Bus h,
Schneider and Walter, ibid. 1903, 36, 3877;
Meussdorffer, J. pr. Chem. 1907, [ii.] 75, 121) ;
substituted ureas (Dixon, Chem. Soc. Trans.
1897, 628) ; magnesium ethyl bromide (Siisskind,
Ber. 1906, 39, 225) ; magnesium phenylamine
iodide (Bodroux, Compt. rend. 1905, 140, 1597).

Dichloroacetic acid CHClg-COOH. Prepared
by chlorinating acetic acid (Maumene, Annalen,
133, 154 ; Miiller, ibid. 159) ; by the interaction
of chloral and potassium cyanide (Wallach, Ber.
1873, 6, 114 ; Annalen, 173, 295 ; Kotz, Chem.
Soc. Abstr. 1910, i. 151) ; by passing chlorine into
phloroglucinol (Hlaziwetz, Annalen, 155, 132 ;
Zincke and Kegel, Ber. 1889, 22, 1476) ; by the
interaction of perchlorethylene and sodium
ethoxide at 120 (Geuther and Fischer, J. 1864,
316) ; of hexachlorotriketohexylene and water
(Zincke and Kegel, I.e.) ; of pyrrol and sodium
hypochlorite (Ciamician and Silber, Ber. 1885,
18, 1764) ; of trichloroacetic acid and sodium
or barium hydroxides (Pinner, ibid. 757) ; by
hydrolysing the ethyl ester (q.v.).

Colourless liquid, m.p. 10-8 (Pickering,
Chem. Soc. Trans. 1895, 667) ; b.p. 189-191 ;
sp.gr. 1-5724 at 13-5 ; mag.rot. (Perkin, ibid.
1896, 1236) ; esterification constant (Sudborough
and Lloyd, Chem. Soc. Trans. 1899, 476).
Slowly decomposed by heating with water in a
sealed tube at 100, more rapidly with sodium or
barium hydroxides {cf. Timofeeff, J. Russ. Phys.
Chem. eoc. 1904, 36, 255). By heating with
silver oxide and a small quantity of water
silver chloride and glyoxylic acid are produced
(Beckurts and Otto, Ber. 1881, 14, 583). On
electrolysis of an aqueous solution hydrogen,
carbon monoxide, carbon dioxide, and an oil
containing chlorine are produced (Troeger and
Ewers, J. pr. Chem. [ii.] 58, 125). The potas-
sium salt yields potassium chloride, trichloro-
acetic acid, and other products on dry distilla-
tion (Frie(hrich, Annalen, 206, 244). Dichloro-
acetic acid reacts with phosphorus pentachloride
(Michael, Amer. Chem. J. 9, 215) ; aniline and
its homologues (Cech and Schwebel, Ber. 1877,
10, 179; HeUer, Annalen, 1904, 332, 247;
1908, 358, 349 ; Ber. 1908, 41, 4264 ; Ostromiss-
lensky, ibid. 1907, 40, 4972; 1908, 41, 3019;
Heller and Aschkenasi, Annalen, 1910, 375,
261) ; thiourea (Dixon, Chem. Soc. Trans. 1893,
816) ; nitrogen sulphide (Francis, ibid. 1905,
1838).

Methyl ester, b.p. 142-144 (Wallach,
Annalen, 173, 299); sp.gr. 1-3808 at 19-2
(Henry, I.e.).

Ethyl ester. Prepared by chlorinating alcohol
(Altschul and Meyer, Ber. 1893, 26, 5757) ; by
the interaction of chloral, alcohol, and potassium
cyanide (Wallach, ibid. 1876, 9, 1212 ; 1877, 10,
1526) ; or of dichlorinated vinyl ethers and
alcohol (D. R. PP. 209268, 210502, 212592;
Chem. Soc. Abstr. 1909, i. 453, 694, 873) ; b.p.
157-7 at 754-6 mm. (Schiff, Annalen, 220, 108) ;
sp.gr. 1-2821 at 20/4 (Bruhl, ibid. 203, 22).
With sodium or silver it yields maleic ester
(Tanatar, Ber. 1879, 12, 1563).

Trichloroacetic acid CCI3-COOH. Prepared
by chlorinating acetic acid in the sunlight
(Dumas, Annalen, 32, 101) ; by the oxidation



HALOGEN ACETIC ACIDS



31



of chloral with fuming nitric acid (Kolbe, ibid.
54, 183; Clermont, Ann. Chim. Phys. [vi.J 6,
135 ; Judson, Ber. 1870, 3, 782 ; Thurnlackh,
A nalen, 210, 63 ; Tommasi and Meldola, Chem.
Soc. Trans. 1874, 314), chromic acid (Clermont,
Compt. rend. 76, 774), or potassium permanga-
nate (Clermont, ibid. 86, 1270).

M.p. 57 (Sudborough and Lloyd, Chem. Soc.
Trans. 1899, 476) ; sp.gr. 1-6298 at 60-6 ; heat
of combustion (const, press.) 92*8 Cals. (Berthelot,
Ann. Chim. Phys. [vi.] 28, 569) ; electrical
conductivity (Rivals, Compt. rend. 125, 274 ;
Ostwald, Zeitsch. physikal. Chem. 1, 100 ; 3,
177 ; Carrara, Gazz. chim. ital. 27, i. 207) ;
esterification constant (Sudborough and Lloyd,
I.e. ; Kailan, Monatsh. 1908, 29, 799) ; mag.rot.
(Perkin, Chem. Soc. Trans. 1896, 1236). At
300 it decomposes into triacetyl chloride,
carbon dioxide, and hydrogen chloride (Engler
and Steude, Ber. 1893, 26, 1443), whilst the
silver salt yields the anhydride, silver chloride,
carbon monoxide, and carbon dioxide (Beckurts
and Otto, Ber. 1881, 14, 576) ; for sodium salt,
cf. Henry, ibid. 1879, 12, 1844. At 200 with
iodine trichloride perchloromethane, hydrogen
chloride, and carbon dioxide are produced
(Krafft, ibid. 1876, 9, 1049). Chloroform and
carbon dioxide are produced by heating the acid
with water or alkalis (Dumas, I.e. ; Otto, Ber.
1871, 14, 589; Seubert, ibid. 1875, 18, 3342),
potassium cyanide (Bourgoin, Compt. rend. 94,
448), aniline (Goldschmidt and Braiier, Ber.
1906, 39, 109), tertiary bases (Silberstein, ibid.
1881, 17, 2664), antipyrine (StoUe, Ber. Deut.
pharm. Ges. 1910, 20, 371), or with resorcinol
or cresol, but phenol or thymol yield hydrogen
chloride, carbon monoxide, and phosgene
(Anselmino, ibid. 16, 390). Reduction with
potassium amalgam or hydriodic acid gives
acetic acid. The sodium or zinc salt yields on
electrolysis trichloro methyl trichloroacetate (Elbs
and Kratz, J. pr. Chem. [ii.] 55, 502). For
compounds with aldehydes and ketones, v.
Koboseff, J. Russ. Phys. Chem. Soc. 1903, 35,
652; PlotnikofE, ibid. 1904, 36, 1088; 1905,
37, 875 ; Ber. 1906, 39, 1794).

Methyl ester. B.p. 152-3-152-5 at 765-3 mm.
(Schiff, Zeitsch. physikal. Chem. 1, 379; cf.
Anschutz and Haslam, Annalen, 253, 124) ;
sp.gr. 1-4892 at 19-2 (Henry, J. 1885, 1329).

Jthyl ester. Prepared by the interaction of
trichloroacetic acid and alcohol with sulphuric
acid (Clermont, Compt. rend. 1901, 133, 737),
or with hydrogen chloride (Spiegel, Ber. 1907,
40, 1730) ; b.p. 164 ; sp.gr. 1-369 at 15 (Claus,
Annalen, 191, 58 ; Bruhl, ibid. 203, 22 ; SchifE,
ibid. 220, 108). With ammonia it yields the
amide ; with sodium ethoxide, orthoformic ester,
sodium ethyl carbonate, and sodium chloride are
the products (Klein, Chem. Soc. Trans. 1877,
i. 291.

Beomoacetic Acids.

Monobromoacetic acid CHaBr-COOH. Pre-
pared by the action of bromine on acetic acid,
either alone (Perkin and Duppa, Annalen, 108,
1(j6) or in the presence of carbon disulphide
(Michael, Amer. Chem. J. 5, 202), or of sulphur
(Genvresse, Bull. Soc. chim. [iii.] 7, 364); by
the interaction of chloroacetic and hydrobromic
acids at 150 (Demole, Ber. 1876, 561) ; by the
oxidation of ethylene dibromide with fuming
sulphuric acid (Kachler, Monatsh. 2, 559), or



of monobro mo acetylene in alcoholic solution by
air (Glockner, Annalen, Suppl. 7, 115).

M.p. 49-50; b.p. 117-118/15 mm.
(Sudborough and Lloyd, Chem. Soc. Trans.
1899, 477), 196 (Lassar-Cohn, Annalen, 251,
342). On heating an aqueous solution of the
acid it is slowly decomposed into glycoUic acid
(Senter, Chem. Soc. Trans. 1909, 1828). Electrical
conductivity (Ostwald, Zeitsch. physikal. Chem.
3, 178 ; Kortright, Amer. Chem. J. 18, 368).
By heating the acid with silver powder at 130,
succinic acid is formed, whilst with silver nitrate
silver glycollate is produced (Senter, Chem. Soc.
Trans. 1910, 346). Nitrogen sulphide yields
bromoacetamide and bromodiacetamide (Fran-
cis, ibid. 1905, 1839). The sodium salt heated
in vacuo yields glycollide. The potassium salt
gives on electrolysis acetic acid, bromine, and
carbon dioxide, no hydrogen being evolved until
the potassium salt is completely decomx^oscd
(Lassar-Cohn, I.e.). Monobromoacetic acid has
been used as a reagent for detecting albumin in
urine (Boymond, J. Pharm. Chim. [v.] 20, 482).

Methyl ester. Prepared by heating methyl
alcohol and monobromoacetic acid in sealed
tubes at 100 (Perkin and Duppa, Annalen,
108, 109) ; b.p. 144.

Ethyl ester. Prepared as methyl ester, or
together with other products by the interaction
of sodium ethoxide and bromine (Sell and
Salzmann, Ber. 1874, 7, 496); b.p. 159. It
undergoes numerous condensations : with mag-
nesium it yields ethyl acetoacetate and ethyl y-
bromoacetoacetate (Stolle, Ber. 1908, 41, 9j4) ;
with ethyl oxalylacetate, ethyl citrate (LaAvrence,
Chem. Soc. Trans. 1897, 458); with ethyl
sodioacetoacetate, ethyl acetosuccinate (Sprank-
ling, ibid. 1165); Avith ethyl dimethylacetoace-
tate, ethyl oa)8-trimethyl-;8-hydroxyglutarate
(Perkin and Thorpe, ibid. 1178).

For other esters, v. Clarke, ibid. 1910, 428 ;
Steinlen, Bull. Acad. roy. Belg. [iii.] 34, 101 ;
Kunckell and Scheven, Ber. 1898, 31, 172).

Dibromoacetlc acid CHBr^'COOH. Prepared
by the action of bromine on acetic acid alone
(Perkin and Duppa, Annalen, 110, 115), or in
the presence of sulphur (Genvresse, Bull. Soc.
chim. [iii.] 7, 478) ; by the hydrolysis of the
ethyl ester {q.v.) ; m.p. 48 ; b.p. 232-234 ;
esterification constant, v. Sudborough and Lloyd,
Chem. Soc. Trans. 1899, 477. The silver salt,
heated with water, yields silver bromide,
glyoxylio acid, and dibromoacetic acid (Perkin,
ibid. 1877, i. 91).

Ethyl ester. Prepared by the action of
bromine on ethyl acetate at 160 ; by passing
bromine into alcohol (Schaffer, Ber. 1871, 4,
368) ; by the interaction of 4 parts of bromal
hydrate with 1 part of alcoholic potassium
cyanide (Remi, J. Russ. Phys. Chem. Soc. 7,
263) ; b.p. 192.

Tribromo acetic acid CBrg'COOH. Prepared
by the oxidation of bromal with fuming nitric
acid (Schaffer, Ber. 1871, 4, 370 ; Gal, Compt.
rend. 77, 786) or by heating an aqueous solution
of malonic acid mth bromine (Petriew, Ber.
1875, 8, 730). Monoclinic plates, m.p. 131
(Sudborough and Lloyd, Chem. Soc. Trans.
1899, 477 ; cf. Gal, Annalen, 129, 56) ; electrical
conductivity, v. Swartz, Chem. Zentr. 1898, ii.
703). On heating at 245 bromine and hydrogen
bromide re evolved. By heating an aqueous



32



HALOGEN ACETIC ACIDS.



solution of the acid or its salts, bromoform is
produced. For compounds with aldehydes and
ketones, v. Koboseff, J. Russ. Phys. (Jhem. Soc.
1903, 35, 652; Plotnikoff, ibid. 1908, 40, 64, 1238).
Ethyl ester. Prepared by passing hydrogen
chloride into a cooled alcoholic solution of tri-
bromoacetic acid (Broche, J. pr. Chem. [ii.] 50,
98) ; b.p. 225.

Chlorobkomoacetic Acids.

Chlorobromoacetic acid CHClBr-COOH. Pre-
pared by heating monochloroacetic acid (1 mol.)
with bromine (1 mol.) in sealed tubes at 160
(Cech and Steiner, Ber. 1875, 8, 1174). Pungent
liquid, b.p. 201; ethyl ester, b.p. 160-163 ;
amide, m.p. 126.

Monochlorodibromoacetic acid CClBr./COOH.
Prepared by heating monochlorodibromoacetal-
dehj^de with fuming nitric acid (Neumeister,
Ber. 1882, 15, 603) ; rhombic plates, m.p. 89 ;
b.p. 232-234, with decomposition. Potassium
hydroxide converts it, on heating, into mono-
chlorodibromomethane.

Dichloromonobromoacetic acid CCl^Br-COOH.
Prepared by heating dichlo^^(i^Jlonobromoacetal-
dehyde with fuming nitric acid (Neumeister,
I.e.) ; prisms, m.p. 64 ; b.p. 215 with decompo-
sition ; readily soluble in water or alcohol.
Potassium hydroxide converts it, on heating,
into dichloromonobromomethane.

loDOACETic Acids.

Mono-iodoacetic acid CHgl-COOH. Prepared
by decomposing the ethyl ester {q.v.) Avith baryta
water (Perkin and Duppa, Annalen, 112, 125) ;
by heating acetic anhydride with iodine and
iodic acid (Schiitzenberger, Zeitsch. Chem.
1868, 484). Prismatic needles, m.p. 82;
electrical conductivity (Walden, Zeitsch. physi-
kal. Chem. 1892, 10, 647) ; esterification constant
(Sudborough and Lloyd, Chem. Soc. Trans.
1899, 478).

Methyl ester. Prepared in the same manner
as the ethyl ester (Aronstein and Kramps, Ber.
1881, 14, 604) ; b.p. 169-171.

Ethyl ester. Prepared by the interaction of
ethyl chloro- or bromoacetate, potassium iodide,
and alcohol (Perkin and Duppa, I.e.) ; together
with other products by heating di-iodoacetylene
with excess of alcoholic jDotassium hydroxide
(Nef, Annalen, 298, 348). Colourless oil with a
penetrating smell ; b.p. 69/12 mm. ; 75-
78/16 mm. (Tiemann, Ber. 1898, 31, 825).

Di-iodoacetic acid CHI j- CO OH. Prepared
by the interaction of 1 part of malonic acid
with 1 part of iodic acid in 4 parts of water ;
carbon dioxide is evolved, the solution is cooled,
filtered, and allowed to stand. After 2 or 3
days crystals of tri-iodoacetic acid separate ;
these are filtered off and, after heating the
filtrate, the di-iodo compound separates on
cooling; m.p. 110 (Angeli, Ber. 1893, 26, 596).

Ethyl ester. Prepared by the interaction of
ethyl dibromoacetate and potassium iodide in
alcoholic solution (Perkin and Duppa, Annalen,
117, 351), or of ethyl dichloroacetate and calcium
iodide (Spindler, ibid. 231, 273). Yellow liquid,
which cannot be distilled imchanged under
atmospheric pressure.

Tri-iodoacetic acid Clg-COOH. For prepara-
tion, V. di-iodoacetic acid. Yellow plates, m.p.
150 with decomposition. By heating with



acetic acid iodoform and carbon dioxide are
produced.

HAMAMELIN. A preparation from the
witch-hazel Hamamelis virginiana (Linn.), either
green or brown in colour, c'.epending upon
whether the leaves or bark have been used.

HARDWICKIA RESIN v. Oleo-resins.

HARMALA. The seeds of the wild rue, Pe
ganum Harmala (Linn.), or harmal seeds, have
been employed from the earliest times in Eastern
medicine as a stimulant, anthelmintic, or even
as a narcotic. They are said to be the source
of a red dye produced in Southern Russia, and
they have been used in the manufacture of oil.
Wild rue is an odoriferous herbaceous plant,
1-3 feet high, and inhabits Southern Europe,
Asia Minor, Egypt, North-western India, and
Southern Siberia (Fluckiger, Pharm. J. [iii.] 2,
229).

Harmal seeds contain about 4 p.c. of two
alkaloids (probably in combination with phos-
phoric acid), which are found for the most part
in the outer portions of the seed. The first of
these, harmaline CJ3HJ4N2O was discovered by
Grbel (Annalen, 38, 363), the second, harmine
C13H12N2O by Fritzsche {ibid. 64, 360; J.
1847-8, 639 ; Annalen, 68, 351 ; 68, 355 ; 72,
306 ; 88, 327 ; 88, 328 ; 92, 330 ; J. 1862, 377),
who studied both alkaloids, and obtained
numerous derivatives. Fritzsche extracts the
seeds with water containing acetic or sulphuric
acid, and saturates the solution obtained with
common salt, which causes the alkaloids to
precipitate in the form of hydrochlorides. The
precipitate is dissolved in water, decolorised
by treatment with animal charcoal, and the
solution obtained is fractionally precipitated by
ammonium hydroxide at 50-60. The first
portion of the precipitate is harmine, and the
last portion harmaline. The crude harmaline is
best purified by recrystallisation from methyl
alcohol (O. Fischer and Tauber, Ber. 1^, 400).
From methyl alcohol harmaline crystallises in
small tables, or from ethyl alcohol in rhombic
octahedra. It melts with decomposition at 238.
It is very slightly soluble in cold water or ether,
but readily dissolves in hot alcohol. It forms a
well-defined crystalline hydrochloride
Ci3Hi4N20,HCl,2H20;
hydrocyanide Ci3Hi4N20,HCN ; platinichloride
(Ci 3H1 4N20,HCl)2ptCl4 ; methiodide

C,3Hi4N20,MeI;
chromate (Ci3Hi4N20)2H2Cr04 ; and 7utro
derivative Ci3H^3(N02)N20. Both the hydro-
cyanide and the nitro derivative are bases,
and combine with acids to form crystalline
salts. Nascent hydrogen converts harmaline
into a dihydride C^gHieNaO (0. Fischer, Ber.
22, 638). Harmaline is shown by Fischer (ibid.
28, 2481) to be dihydro- harmine, and it can bo
converted into harmine by oxidation, which is
best effected by potassium permanganate in
dilute sulphuric acid solution. By oxidation
with chromic acid in boiling acetic acid solution
or by nitric acid both harmaline and harmine
are converted into harminic acid CtoH^N204.
By the action of hydrochloric acid on harmahne,
Fischer and Tauber obtained a brick-red crystal-
line powder harmalol CjaHigNgO, which melts
at 212 with decomposition. This compound
also occurs naturally in harmal seeds, and has



HELIUM.



33



been isolated from these by Fischer (Chcm.
Zentr. 1901, i. 957).

Harmino exists in harmal seeds in much
smaller proportion than harmaline. It may,
however, be prepared from the latter by simple
oxidation, either l)y the action of heat on the
dry chromate, or by heating an alcoholic solu-
tion of harmaline nitrate to which hydrochloric
acid has been added. Harmine crystallises in
four-sided prisms (Schabus, J. 1854, 525). It
melts with decomposition at 257-259. It is
very slightly soluble in water or alcohol, and
slightly soluble in ether. The salts of harmine
are crystalline and colourless, and in acid solu-
tion exhibit an indigo blue fluorescence. The
more important are the hydrochloride

Ci3Hi2N20,HCl,2H20;

the platinichloride (Ci3H,2N20,HCl)2PtCl4 ; the
methiodide CigHjaNgOjMel (F. and T.); and
the two sulphates (Ci3H,2N20)2,H2804,H20,
and Ci 31112^20,112804. Fritszche prepared the
following halogen and nitro derivatives of
harmine all of which are bases and form crystal-
line salts: dichloroJuirmine CjgHioClaNgO ;
nitrolmrmine C,3Hi,(N02)N20 ; chloronitrohar-
mine C]3HiCl(N02)N20 ; and hromonitrohar-
mine Ci3HioBr(N02)N20. A tetrabromide

Ci3Hi2N20Br4

has been obtained by Fischer.

When harmine is treated with concentrated
hydrochloric acid at 140, Fischer and Tauber
find that it breaks up into methyl chloride and a
new phenolic compound harmol Ci2HioN20,
which crystallises in needles and melts at 321.
When harmol is fused with potash it yields a
compound possessing both basic and acid pro-
perties, harmolic acid, C12H10N2O5, which melts
at 247 (Fischer, Ber. 22, 637). Fischer and
Tauber, by acting on harmine in acetic acid so-
lution with chromic acid, obtained dibasic har-
minic acid C8H6N2(COOH)2. It forms silky
needles, melting at 345, at which point it de-
composes into carbon dioxide and a crys-
talline basic sublimate of apoharmine C,HgN2
m.p. 183, from which Fischer obtained a well-
defined gold salt. A tetrabromide CgH.5N2Br4,
and a dihydride C8H8N2H2, were also obtained.
Other derivatives of harmine are described by
Fischer and Buck (Ber. 38, 329). . A. S.

HARMALIN. Fuchsin v. Triphenyl me-

THANE COLOURING MATTERS.

HARMALINE, HARMALOL, HARMINE,
HARMINIC ACID, HARMOL and HARMOLIC
ACID, V. Harmala.

HARTIN V. Resins.

HARTITE V. Resins.

HAUERITE. Manganese disulphide MnS^
V. Manganese.

HAUSMANNITE. Trimanganic tetroxide
Mn304 {v. Manganese).

HAZELINE. Trade name for a fragrant es-
sence obtained from the fresh bark of Hama-
melis virginiana (Linn.) or witch-hazel. Is
probably analogous to eucalyptol. Is a colour-
less oil, possessing a pleasant pungent smell and
sweet astringent taste. Is used in the treatment
of eczema, ulcers, burns, &c., and as a substitute
for arnica.

HEAVY SPAR. Native barium sulphate v.
Barytes and Barium.

Vol. III. T.



HEBBAKHADE v. Gum resins.

HECLA POWDER v. Explosives

HEDERIC ACID. An acid contained in ivy
berries ; v. Ivy gum resin, art. Gum resins.

HEDERINE. A poisonous glucoside

C'64Hio40i9 found in ivy. Dextrorotary [a]p
= 16-27. By hydrolysis yields rhamnose and
hederidine C28H40O4 crystallising in rhombic
prisms, m.p. 324, and subliming without



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