(see OXIMES, also A. Hantzsch, Ber., 1891, 24, p. 13). The ketones react
with mercaptan to form mercaptols (E. Baumann, _Ber._, 1885, 18, p.
883), and with concentrated nitric acid they yield dinitroparaffins (G.
Chancel, _Bull. de la soc. chim._, 1879, 31, p. 503). With nitrous acid
(obtained from amyl nitrite and gaseous hydrochloric acid, the ketone
being dissolved in acetic acid) they form isonitrosoketones, R·CO·CH:NOH
(L. Claisen, _Ber._, 1887, 20, pp. 656, 2194). With ammonia they yield
complex condensation products; acetone forming di- and tri-acetonamines
(W. Heintz, _Ann._ 1875, 178, p. 305; 1877, 189, p. 214). They also
condense with aldehydes, under the influence of alkalis or sodium
ethylate (L. Claisen, _Ann._, 1883, 218, pp. 121, 129, 145; 1884, 223,
p. 137; S. Kostanecki and G. Rossbach, _Ber._, 1896, 29, pp. 1488, 1495,
1893, &c.). On treatment with the Grignard reagent, in absolute ether
solution, they yield addition products which are decomposed by water
with production of tertiary alcohols (V. Grignard, _Comptes rendus_,
1900, 130, P. 1322 et seq.),
RR´CO --> RR´·C(OM_(g)I)·R´´ --> RR´R´´·C(OH) + M_(g)I·OH.
Ketones do not polymerize in the same way as aldehydes, but under the
influence of acids and bases yield condensation products; thus acetone
gives mesityl oxide, phorone and mesitylene (see below).
For _dimethyl ketone_ or acetone, see ACETONE. _Diethyl ketone_,
(C2H5)2·CO, is a pleasant-smelling liquid boiling at 102.7° C. With
concentrated nitric acid it forms dinitroethane, and it is oxidized by
chromic acid to acetic and propionic acids. _Methylnonylketone_,
CH3·CO·C9H19, is the chief constituent of oil of rue, which also
contains _methylheptylketone_, CH3·CO·C7H15, a liquid of boiling-point
85-90° C. (7 mm.), which yields normal caprylic acid on oxidation with
hypobromites.
_Mesityl oxide_, (CH3)2C:CH·CO·CH3, is an aromatic smelling liquid of
boiling point 129.5-130° C. It is insoluble in water, but readily
dissolves in alcohol. On heating with dilute sulphuric acid it yields
acetone, but with the concentrated acid it gives mesitylene, C9H12.
Potassium permanganate oxidizes it to acetic acid and
hydroxyisobutyric acid (A. Pinner, _Ber._, 1882, 15, p. 591). It forms
hydroxyhydrocollidine when heated with acetamide and anhydrous zinc
chloride (F. Canzoneri and G. Spica, _Gazz. chim. Ital._, 1884, 14, p.
349). _Phorone_, (CH3)2C:CH·CO·CH:C(CH3)2, forms yellow crystals which
melt at 28° C. and boil at 197.2° C. When heated with phosphorus
pentoxide it yields acetone, water and some pseudo-cumene. Dilute
nitric acid oxidizes it to acetic and oxalic acids, while potassium
permanganate oxidizes it to acetone, carbon dioxide and oxalic acid.
DIKETONES.--The diketones contain two carbonyl groups, and are
distinguished as [alpha] or 1.2 diketones, [beta] or 1.3 diketones,
[gamma] or 1.4 diketones, &c., according as they contain the groupings
-CO·CO-, -CO·CH2·CO-, -CO·CH2·CH2·CO-, &c.
The [alpha]-diketones may be prepared by boiling the product of the
action of alkaline bisulphites on isonitrosoketones with 15% sulphuric
acid (H. v. Pechmann, _Ber._, 1887, 20, p. 3112; 1889, 22, p. 2115),
CH3·CO·C:(N·OH)·CH3 --> CH3·CO·C:(NHSO3)·CH3 --> CH3·CO·CO·CH3; or by
the action of isoamyl nitrite on the isonitrosoketones (O. Manasse,
_Ber._, 1888, 21, p. 2177), C2H5·CO·C = (NOH)·CH3 + 11C5HONO =
C2H5·CO·CO·CH3 + C5H11OH + N2O. They condense with orthodiamines to
form quinoxalines (O. Hinsberg, _Ann._, 1887, 237, p. 327), and with
ammonia and aldehydes to form imidazoles. _Diacetyl_, CH3·CO·CO·CH3,
is a yellowish green liquid, which boils at 87-88°C., and possesses a
pungent smell. It combines with sodium bisulphite and with hydrocyanic
acid. Dilute alkalis convert it into paraxyloquinone.
The [beta]-diketones form characteristic copper salts, and in
alcoholic solution they combine with semicarbazide to form products
which on boiling with ammoniacal silver nitrate solution give
pyrazoles (T. Posner, _Ber._, 1901, 34, p. 3975); with hydroxylamine
they form isoxazoles, and with phenylhydrazine pyrazoles. _Acetyl
acetone_, CH3·CO·CH2·CO·CH3, may be prepared by the action of
aluminium chloride on acetyl chloride, or by condensing ethyl acetate
with acetone in the presence of sodium (L. Claisen). It is a liquid of
boiling point 136° C. It condenses readily with aniline to give
[alpha][gamma]-dimethyl quinoline.
The [gamma]-diketones are characterized by the readiness with which
they yield furfurane, pyrrol and thiophene derivatives, the furfurane
derivatives being formed by heating the ketones with a dehydrating
agent, the thiophenes by heating with phosphorus pentasulphide, and
the pyrrols by the action of alcoholic ammonia or amines. _Acetonyl
acetone_, CH3·CO·CH2·CH2·CO·CH3, a liquid boiling at 194° C., may be
obtained by condensing sodium aceto-acetate with mono-chloracetone (C.
Paal, Ber., 1885, 18, p. 59),
CH3COCH2Cl + Na·CH·COCH3(COOR)
--> CH3CO·CH2·CH·COCH3(COOR)
--> CH3CO·CH2·CH2·COCH3;
or by the hydrolysis of diaceto-succinic ester, prepared by the action
of iodine on sodium aceto-acetate (L. Knorr, _Ber._, 1889, 22, pp.
169, 2100).
1.5 diketones have been prepared by L. Claisen by condensing
ethoxymethylene aceto-acetic esters and similar compounds with
[beta]-ketonic esters and with 1.3 diketones. The ethoxymethylene
aceto-acetic esters are prepared by condensing aceto-acetic ester with
ortho-formic ester in the presence of acetic anhydride (German patents
77354, 79087, 79863). The 1.5 diketones of this type, when heated with
aqueous ammonia, form pyridine derivatives. Those in which the keto
groups are in combination with phenyl residues give pyridine
derivatives on treatment with hydroxylamine, thus benzamarone,
C6H5CH[CH(C6H5)·CO·C6H5], gives pentaphenylpyridine, NC5(C6H5)5. On
the general reactions of the 1.5 diketones, see E. Knoevenagel
(_Ann._, 1894, 281, p. 25 et seq.) and H. Stobbe (_Ber._, 1902, 35, p.
1445).
Many cyclic ketones are known, and in most respects they resemble the
ordinary aliphatic ketones (see POLYMETHYLENES; TERPENES).
KETTELER, WILHELM EMMANUEL, BARON VON (1811-1877), German theologian and
politician, was born at Harkotten, in Bavaria, on the 25th of December
1811. He studied theology at Göttingen, Berlin, Heidelberg and Munich,
and was ordained priest in 1844. He resolved to consecrate his life to
maintaining the cause of the freedom of the Church from the control of
the State. This brought him into collision with the civil power, an
attitude which he maintained throughout a stormy and eventful life.
Ketteler was rather a man of action than a scholar, and he first
distinguished himself as one of the deputies of the Frankfort National
Assembly, a position to which he was elected in 1848, and in which he
soon became noted for his decision, foresight, energy and eloquence. In
1850 he was made bishop of Mainz, by order of the Vatican, in preference
to the celebrated Professor Leopold Schmidt, of Giessen, whose Liberal
sentiments were not agreeable to the Papal party. When elected, Ketteler
refused to allow the students of theology in his diocese to attend
lectures at Giessen, and ultimately founded an opposition seminary in
the diocese of Mainz itself. He also founded orders of School Brothers
and School Sisters, to work in the various educational agencies he had
called into existence, and he laboured to institute orphanages and
rescue homes. In 1858 he threw down the gauntlet against the State in
his pamphlet on the rights of the Catholic Church in Germany. In 1863 he
adopted Lassalle's Socialistic views, and published his _Die Arbeitfrage
und das Christenthum_. When the question of papal infallibility arose,
he opposed the promulgation of the dogma on the ground that such
promulgation was inopportune. But he was not resolute in his opposition.
The opponents of the dogma complained at the very outset that he was
wavering, half converted by his hosts, the members of the German College
at Rome, and further influenced by his own misgivings. He soon deserted
his anti-Infallibilist colleagues, and submitted to the decrees in
August 1870. He was the warmest opponent of the State in the
_Kulturkampf_ provoked by Prince Bismarck after the publication of the
Vatican decrees, and was largely instrumental in compelling that
statesman to retract the pledge he had rashly given, never to "go to
Canossa." To such an extent did Bishop von Ketteler carry his
opposition, that in 1874 he forbade his clergy to take part in
celebrating the anniversary of the battle of Sedan, and declared the
Rhine to be a "Catholic river." He died at Burghausen, Upper Bavaria, on
the 13th of July 1877. (J. J. L.*)
KETTERING, a market town in the eastern parliamentary division of
Northamptonshire, England, 72 m. N.N.W. from London by the Midland
railway. Pop. of urban district (1891), 19,454; (1901), 28,653. The
church of SS Peter and Paul, mainly Perpendicular, has a lofty and
ornate tower and spire. The chief manufactures are boots, shoes,
brushes, stays, clothing and agricultural implements. There are
iron-works in the immediate neighbourhood. The privilege of market was
granted in 1227 by a charter of Henry III.
KETTLE, SIR RUPERT ALFRED (1817-1894), English county court judge, was
born at Birmingham on the 9th of January 1817. His family had for some
time been connected with the glass-staining business. In 1845 he was
called to the bar, and in 1859 he was made judge of the Worcestershire
county courts, becoming also a bencher of the Middle Temple (1882). He
acted as arbitrator in several important strikes, and besides being the
first president of the Midland iron trade wages board, he was largely
responsible for the formation of similar boards in other staple trades.
His name thus became identified with the organization of a system of
arbitration between employers and employed, and in 1880 he was knighted
for his services in this capacity. In 1851 he married; one of his sons
subsequently became a London police magistrate. Kettle died on the 6th
of October 1894 at Wolverhampton.
KETTLEDRUM[1] (Fr. _timbales_; Ger. _Pauken_; Ital. _timpani_; Sp.
_timbal_), the only kind of drum (q.v.) having a definite musical pitch.
The kettledrum consists of a hemispherical pan of copper, brass or
silver, over which a piece of vellum is stretched tightly by means of
screws working on an iron ring, which fits closely round the head of the
drum. In the bottom of the pan is a small vent-hole, which prevents the
head being rent by the concussion of air. The vellum head may thus be
slackened or tightened at will to produce any one of the notes within
its compass of half an octave. Each kettledrum gives but one note at a
time, and as it takes some little time to alter all the screws, two or
three kettledrums, sometimes more, each tuned to a different note, are
used in an orchestra or band. For centuries kettledrums have been made
and used in Europe in pairs, one large and one small; the relative
proportions of the two instruments being well defined and invariable.
Even when eight pairs of drums, all tuned to different notes, are used,
as by Berlioz in his "Grand Requiem," there are still but the two sizes
of drums to produce all the notes. Various mechanisms have been tried
with the object of facilitating the change of pitch, but the simple
old-fashioned model is still the most frequently used in England. Two
sticks, of which there are several kinds, are employed to play the
kettledrum; the best of these are made of whalebone for elasticity, and
have a small wooden knob at one end, covered with a thin piece of fine
sponge. Others have the button covered with felt or india-rubber. The
kettledrum is struck at about a quarter of the diameter from the ring.
The compass of kettledrums collectively is not much more than an
octave, between [music notes]; the larger instruments, which it is
inadvisable to tune below F, take any one of the following notes:--
[Music notes].
and the smaller are tuned to one of the notes completing the chromatic
and enharmonic scale from [music notes]. These limits comprise all the
notes of artistic value that can be obtained from kettledrums. When
there are but two drums--the term "drum" used by musicians always
denotes the kettledrum--they are generally tuned to the tonic and
dominant or to the tonic and subdominant, these notes entering into
the composition of most of the harmonies of the key. Formerly the
kettledrums used to be treated as transposing instruments, the
notation, as for the horn, being in C, the key to which the
kettledrums were to be tuned being indicated in the score. Now
composers write the real notes.
The tone of a good kettledrum is sonorous, rich, and of great power.
When noise rather than music is required uncovered sticks are used.
The drums may be muffled or _covered_ by placing a piece of cloth or
silk over the vellum to damp the sound, a device which produces a
lugubrious, mysterious effect and is indicated in the score by the
words _timpani coperti_, _timpani con sordini_, _timbales_
_couvertes_, _gedämpfte Pauken_. Besides the beautiful effects
obtained by means of delicate gradations of tone, numerous rhythmical
figures may be executed on one, two or more notes. German drummers who
were renowned during the 17th and 18th centuries, borrowing the terms
from the trumpets with which the kettledrums were long associated,
recognized the following beats:--
[Illustration: Music notes.