See also:

• RC (:N•OH)R'-RC(OH)

RC (:N•OH)R'-RC(OH)  :NR' RCONHR' . As regards the constitution of the See also:

• OXIMES

oximes, two possibilities exist, namely>C: NOH, or > Cc oH, and the first of these is presumably correct, since on alkylation and subsequent See also:

• HYDROLYSIS (Gr. 6Swp, water, Anew, to loosen)

hydrolysis an alkyl See also:

• HYDROXYLAMINE, NH2OH

hydroxylamine of the type See also:

• NH2

NH2.OR is obtained, and consequently it is to be presumed that in the alkylated oxime, the alkyl See also:

• GROUP

group is attached to See also:

• OXYGEN (symbol 0, atomic weight 16)

oxygen, and the oxime itself therefore contains the hydroxyl group . It is to be noted that the oximes of aromatic See also:

• ALDEHYDES

aldehydes and of unsymmetrical aromatic See also:

• KETONES

ketones frequently exist in isomeric forms . This See also:

• ISOMERISM

isomerism is explained by the Hantzsch-See also:

• WERNER, ABRAHAM GOTTLOB (1750-1817)
• WERNER, ANTON ALEXANDER VON (1843– )
• WERNER, FRIEDRICH LUDWIG ZACHARIAS (1768–1823)

Werner See also:

• HYPOTHESIS (from Gr. inrorcOivat, to put under; cf. Lat. suppositio, from sub-ponere)

hypothesis (Ber., 189o, 23, p . II) in which the See also:

• ASSUMPTION, FEAST OF

assumption is made that the three valencies of the See also:

• NITROGEN [symbol N., atomic weight 14.01, 0=16]

nitrogen See also:

• ATOM (Gr. &rows, indivisible, from a- privative, and TE,aPfw, to cut)

atom do not See also:

• LIE, JONAS LAURITZ EDEMIL (1833—1908)
• LIE, MARIUS SOPHUS (1842–1899)

lie in the same See also:

• PLANE

plane . Thus in the See also:

• CASE
• CASE, JOHN (d. 1600)

case of the See also:

• SIMPLE

simple aldoximes two See also:

• CON

con- R•C•H R.C.H figurations are possible, namely : and • • , the former, N.OH HO.N where the H atom and OH group are contiguous, being known as syn-aldoximes and the latter as the See also:

• ANTI, or CAMPA

anti-aldoximes . The syn-aldoximes or treatment with acetyl chloride readily lose See also:

• WATER

water and yield nitrites; the anti-aldoximes as a See also:

• RULE

rule are acetylated and do not yield nitrites . The isomerism of the oximes of unsymmetrical ketones is explained in the same manner, and their configuration is determined by an application of the See also:

• BECKMANN, JOHANN (1739–1811)

Beckmann transformation (see Ber., 1891, 24, p . 13); thus: R•C•R' --> R•C (OH) : NR'--> R•CONHR'(R' and OH, " syn ") . N•OH R•C•R' —> RN : C(OH)R'—>RNH.See also:

• COR

COR' (R and OH," syn") . HO.N Aldoximes are generally obtained by the See also:

• ACTION

action of hydroxylamine hydrochloride on the aldehyde in presence of See also:

• SODIUM [symbol Na, from Lat. natrium; atomic weight 23.00 (0=16)]

sodium carbonate; the oxime being then usually extracted from the See also:

• SOLUTION (from Lat. solvere, to loosen, dissolve)

solution by See also:

• ETHER, (C2H5)2O

ether . They may also be prepared by the reduction of See also:

• PRIMARY

primary nitro compounds with stannous chloride and concentrated hydrochloric See also:

• ACID (from the Lat. root ac-, sharp; acere, to be sour)

acid; by by the reduction of unsaturated nitro compounds with See also:

• ALUMINIUM (symbol Al; atomic weight 27.0)

aluminium See also:

• AMALGAM

amalgam or See also:

• ZINC

zinc dust in the presence of dilute acetic acid (L .

Bouveault, Comptes rendus, 1902, 134, p . 1145) : %C:CHNO2-R2C: CH . NHOH - R2CH• CH : NOH, and by the action of alkyl iodides on the sodium See also:

• SALT (a common Teutonic word, cf. Dutch zout, Ger. Salz, Scand. salt; cognate with Gr. &Xs, Lat. sal)
• SALT, SIR TITUS, BART

salt of nitro-hydroxylamine (A . Angeli, Rend . Acad. d . Lincei, 1905, (5), 14, ii. p . 411), the See also:

• CYCLE
• CYCLE (Gr. KUK)^os, a circle)

cycle of reactions probably being as follows: NO2•NHOH—>HNO2+HNO; HNO+RI—MHI+RNO (CH3CH2NO-CH3CII: N.OH) . Formaldoxime, See also:

• CH2
• CH2(OH)

CH2: NOH, was obtained by W . R . See also:

• DUNSTAN, SAINT (924 or 925-g88)

Dunstan (Jour . Chem . See also:

• SOC

Soc., 1898, 73, p .

352) as a colourless liquid by the addition of hydroxylamine hydrochloride to an aqueous solution of formaldehyde in the presence of sodium carbonate; the resulting solution was extracted with ether and the oxime hydrochloride precipitated by gaseous hydrochloric acid, the precipitate being then dissolved in water, the solution exactly neutralized and distilled . It boils at 83-85° C. and See also:

• BURNS, JOHN (1858– )
• BURNS, ROBERT (1759-1796)
• BURNS, SIR GEORGE

burns with a See also:

• GREEN, A
• GREEN, ALEXANDER HENRY (1832—1896)
• GREEN, DUFF (1791—1875)
• GREEN, JOHN RICHARD (1837—1883)
• GREEN, MATTHEW (1696-1737)
• GREEN, THOMAS HILL (1836-1882)
• GREEN, VALENTINE (1739–1813)
• GREEN, WILLIAM HENRY (.1825–1900)

green coloured See also:

• FLAME (Lat. flamma; the root flag- appears in flagrare, to burn, blaze, and Gr. d, XEryew)

flame . It is readily transformed into a solid polymer, probably (CH2: NOH)3 . In the See also:

• ABSENCE (Lat. absentia)

absence of water, it forms salts of the type (CH2: NOH)3•HCI with acids . It behaves as a powerful reducing See also:

• AGENT (from Lat. agere, to act)

agent, and on hydrolysis with dilute See also:

• MINERAL

mineral acids is decomposed into formaldehyde and hydroxylamine, together with some formic acid and See also:

• AMMONIA (NH3)

ammonia, the amount of each product formed varying with temperature, See also:

• TIME (0. Eng. Lima, cf. Icel. timi, Swed. timme, hour, Dan. time; from the root also seen in " tide," properly the time of between the flow and ebb of the sea, cf. O. Eng. getidan, to happen, " even-tide," &c.; it is not directly related to Lat. tempus)
• TIME, MEASUREMENT OF
• TIME, STANDARD

time of reaction, amount of water See also:

• PRESENT

present, &c . This latter reaction is probably due to some of the oxime existing in the See also:

• FORM (Lat. forma)

form of the isomeric formamide HCO•NH2 . Acetyl- and benzoyl-formaldoxime are derivatives of the threefold polymeric form . The acetyl See also:

• COMPOUND
• COMPOUND (from Lat. componere, to combine or put together)

compound on reduction yields two of its nitrogen atoms in the form of ammonia and the third in the form of methylamine . Acetaldoxime, CH3CH: NOH, crystallizes in needles which melt at 47° C . On continued See also:

• FUSION

fusion the melting point gradually sinks to about 13° C., probably owing to See also:

• CONVERSION (Lat. conversio, from convertere, to turn or ,change)

conversion into a polymeric form . Chloraloxime, CC13CH : NOH, is obtained when one molecular proportion of See also:

• CHLORAL

chloral See also:

• HYDRATE

hydrate is warmed with four molecular See also:

• PRO

pro-portions of hydroxylamine hydrochloride and a little water . It crystallizes in prisms which melt at 39° C .

A chloral hydroxylamine, CCI3•CHOH•NHOH, melting at 98° C. is obtained by allowing a mixture of one molecular proportion of chloral hydrate with two molecular proportions of hydroxylamine hydrochloride and one of sodium carbonate to stand for some time in a desiccator . Glyoxime, HON:CH•CH:NOH, obtained from glyoxal and hydroxylamine, or by boiling amidothiazole with excess of hydroxylamine hydrochloride and water, melts at 178° C. and is readily soluble in hot water . Succinic aldehyde dioxime, HON: CH.CH2.CH2.CH: NOH, is obtained by boiling an alcoholic solution of See also:

• PYRROL, C4H5N

pyrrol with hydroxylamine hydrochloride and anhydrous sodium carbonate (G . Ciamician, Ber., 1884, 17, p . 534) . It melts at 173° C.; and on reduction with sodium in alcoholic solution yields tetramethylene diamine . A boiling solution of See also:

• CAUSTIC (Gr. rcavvraubs, burning)

caustic potash hydrolyses it to ammonia and succinic acid . Benzaldoximes.—The a-oxime (benz-anti-aldoxime) is formed by the action of hydroxylamine on See also:

• BENZALDEHYDE (oil of bitter almonds), C6H5CHO

benzaldehyde . It melts at 35° C and boils at 117° C . (14 mm.) . Acids convert it into the ,B-oxime (benz-syn-aldoxime) which melts at 125° C . When distilled under diminished pressure the fl-form reverts to the a-modification (see Beckmann, Ber., 1887, 20, p .

2766; 1889, 22, pp . 429, 513, 1531, 1588) . Ketoximes are usually rather more difficult to prepare than aldoximes, and generally require the presence of a fairly concentrated alkaline solution . They may also be prepared by the reduction of pseudo-nitrols (R . See also:

• SCHOLL, AURELIEN (1833- )

Scholl, Ber., 1896, 29, p . 87), the reaction probably being : RR : C(NO2)NO—ERR: C: (NHOH)2—)RR: C: NOH+NH2OH . Acetoxime, (See also:

• CH3

CH3)2C:NOH, melts at 58-59° C. and is readily soluble in water . Its sodium salt is obtained by the action of sodamide on the oxime, in presence of See also:

• BENZENE, C6H6

benzene (A . W . Titherley, Jour . Chem . Soc., 1897, 71, p .

461) . Mesityl oxime, (CH3)2C: CH•C(: NOH) CH3, exists in two modifications . The 0-form is obtained by the See also:

• DIRECT

direct action of hydroxylamine hydrochloride on mesityl See also:

• OXIDE

oxide, the hydrochloride so formed being decomposed by sodium carbonate . It crystallizes in plates which melt at 48-49 C. and See also:

• BOIL

boil at 92° C . (9 mm.) . When boiled for some time with caustic soda, it is converted into the oily a-oxime, which boils at 83-84° C . (9 mm.) . Both forms are volatile in See also:

• STEAM
• STEAM (0. Eng. steam, vapour, smoke, cf. Du. steam; the origin is unknown)

steam . The a-oxime, on See also:

• LONG, GEORGE (1800-1879)
• LONG, JOHN DAVIS (1838– )

long continued boiling with a concentrated solution of a caustic See also:

• ALKALI

alkali, is partially decomposed with formation of some See also:

• ACETONE, or DIMETHYL KETONE

acetone and acetoxime (C . Harries, Ber., 1898, 31, pp . 1381, 1808; 1899, 32, p . 1331) .

By the direct action of hydroxylamine on a methyl See also:

• ALCOHOL

alcohol solution of mesityl oxide in the presence of sodium methylate a hydroxylamino - ketone, diacetone hydroxylamine, (CH3)2C(NHOH) CH2000H3,isformed . In a similar mannerpphorone gives rise to triacetone hydroxylamine, CO:[CH2•C(CH3)2]2:NOH . Acetophenoneoxime, See also:

• C6H5

C6H5.C(:NOH)•CH3, melts at 59° C . In glacial acetic acid solution, on the addition of concentrated sulphuric acid, it is converted into acetanilide . See also:

• BENZOPHENONE (DIPIENYL KETONE)

Benzophenone oxime, CeH6C (:NOH)See also:

• C6H6

C6H6, exists only in one modification which melts at 14o° C.; whereas the unsymmetrical benzophenones each yield two oximes . O . Wallach (See also:

• ANN

Ann., 1900, 312, p . 171) has shown that the saturated cyclic ketones yield oximes which by an application of the Beckmann reaction are converted into isoximes, and these latter on hydrolysis with dilute mineral acids are transformed into acyclic amino-acids; thus from cyclohexanone, e-amidocaproic acid (E-leucine) may be obtained : CH2\CH2•CH2/C: NOH —~ CH2NCH2•CH2•NH CH2\CH2•CH2•NHH An ingenious application of the fact that oximes easily lose the elements of water and form nitrites was used by A . Wohl (Ber., 1893, 26, p . 730) in the " breaking down " of the sugars . Glucoseoxime on warming with acetic anhydride is simultaneously acetylated and dehydrated, yielding an acetylated gluconitrile, which when warmed with ammoniacal See also:

• SILVER

silver nitrate loses hydrocyanic acid and is transformed into an acetyl pentose . The pentose is then obtained from the acetylated compound by successive treatment with ammonia and dilute acids: See also:

• CH2OH

CH2OH•(CHOH)3•CHOH•CH: NOH-CH2OH•(CHOH)3 .

CHOH•CN-CH2OH(CHOH),•CHO . In See also:

• ORDER
• ORDER (through Fr. ordre, for earlier ordene, from Lat. ordo, ordinis, rank, service, arrangement; the ultimate source is generally taken to be the root seen in Lat. oriri, rise, arise, begin; cf. " origin ")
• ORDER, HOLY

order to arrive at the configuration of the stereoisomeric ketoximes, A . Hantzsch (See also:

• BEE (Sanskrit blza, AS. ben, Lat. apis)

Bee., 1891, 24, p . 13) has made use of the Beckmann reaction, whereby they are converted into acid-amides . Thus, with the tolylphenylketoximes, one yields the anilide of toluic acid and the other the toluidide of benzoic acid, the former necessitating the presence of the phenyl and hydroxyl radicals in the syn position and the latter the tolyl and hydroxyl radicals in the syn position, thus: CH, C,See also:

• H4(Sr, Ba, Ca)Al2(SiOa)6+31420. H 4CaAl2(SiO3)

H4 C C6H6 CH3C6H,CONHC6H6; N.OH Syn-phenyltolylketoxime CH3•See also:

• C6H4
• C6H4(CH213r)2

C6H4•C•C6H6 HON CH3C6H4NH0006H6 Anti-tolylphenylketoxime In the case of the aldoximes, that one which most readily loses the elements of water on dehydration is assumed to contain its hydroxyl See also:

• RADICAL (Lat. radix, a root)

radical adjacent to the movable See also:

• HYDROGEN [symbol H, atomic weight x-oo8 (0=16)]

hydrogen atom and is designated the syn-compound . On the oxyamido-oximes see H . Ley, Ber., 1898, 31, p . 2126; G . Schroeter, Ber., 1900, 33, p . 1975 .