A Manual of the Chemistry of the Carbon Compounds; or, Organic Chemistry

521 Pages·11.701 MB·English

by  Schorlemmer C.

A MANUAL OF THE
T HE C A R B ON C O M P O t l N D S;
Olt,
ORGANIC CHEMISTRY.
BY
0. S0HOULEMMEB,, F.R.S.,
OH OBQAK1O CUKM18TRY IN THE 0WEN9 COLtKOB, MANCHESrEB.
MACMILLAN AND CO.
1874.
I¥ht Riirht of Translation and Bepro^ottUm is reserved.]
MNDON:
a. CLAT. WOT. AKD t«WB, PB1NIKH3,
MUSAD nWET HILU
PREFACE.
THE arrangement adopted in this volume is that which I
have followed in my lectures during the last few years.
My endeavour has been to render this work as complete
a record as possible of the present state of organic che-
mistry, which, owing to toe rapid and brilliant develop-
ment of this branch of science, is a somewhat difficult
task.
Of the immense number of organic compounds now
known, only those have been, described which have either
a special theoretical interest or are of importance in
medicine or the arts.
My best thanks are due to my friend, R. S. Dale, B.A.,
for the aid he has rendered rae in writing this book.
C. 8CH0RLEMMEE.
December 1873.
CONTENTS.
PlOK
INTRODUCTION • ... I
QUANTIVALENCE OF ELEMENTS 8
CHEMIOAI, NATURE OP CABBOH ... ... ... ... ... 3
CONSTITUTION OF THE CARBON COMPOUNDS 7
ULTIMATE ANALYSIS OF CARBON COMPOUNDS 15
Determination of Carbon and Hydrogen ... ... .. .. 15
Determination of Nitrogen ... ... ... ... ... 18
Determination of other Elemonts ... ... ... ... ... 19
Calculation of the Analysis ... ... ... ... ... 20
DETERMINATION °* TOE VAPOUR DENSITY ... .. ... ... 21
DETERMINATION OF THE MOLECULAR FOBMITLA 25
EMPIRICAL, RATIONAL, AND CONSTITUTIONAL FORMULiE ... 29
ISOMERISM 82
PHYSICAL PROPERTIES OP THE CARBON COMPOUNDS 85
Speoific Gravity.—Melting Point ami Boiling Point.—Optical Pro-
portics.—Colour, Odour, and Twto.—Solubility.
FRACTIONAL DISTILLATION ... ... ... ... ... ... 45
CLASSIFICATION OF THE CARBON COMPOUNDS 47
OYASOGEN COMPOUNDS 48
Cyanogon Gas.—Cyanogen Hydride.—Afotultio Cyanides.^Forro- awl
Ferricyanidos — Nitroprnaaldca. — Platiuocyanides. ~ Compounds of
Cyanogon with Haloid Eiomonta. -Cyanic Acid and Cyanatos.—Sulpha-
cyanic Acid and Snlphocyanatcs.—Amides of Cyanogon.—Phosphorus
Tricyanide.
CARBONYL AND 8ULPHOCARBONYJL COMPOUNDS 62
Curbon Monoxide—Carbonic Dioxide.—Carbonio Acid nnd Carbonates.
—Gwlionyl Chloride.—Cnrbamie Aoid. — Carbamide or Urea.—Biurot.—
Isurotiua.—Hydroxyl-Carbamide.—Carbouyl Sulphide.—Cwbon Dianl-
pliiilo.—Sulpliocarbonio Add.—Sulphlir.Uroa.
Amos FU^M PoT*sstusi CutRoxiDK ... ,. ... ,„ ... GB
vfii C0NTENT9.
MOB
PARAFFINSOB HYDROCARBONS OF THE SERIES C H,,+, ... 70
n
COMPOUNDS OF MONAD RADICALS ,.. 16
Parsuur ALOOHOIS AND FATTY ACIDS ... .. 80
SECONDARY ALOOHOM AND KRTOSES ... ... ... ... 86
TRRTIARY ALCOHOLS ... ... ... ... ... ... 88
METHYL COMPOUNDS ... ... ... ... ... ... 90
Methyl Aloohol.—Methyl Cyanides.—Nitrogmi Bajes,—Phosphorus
Bosos.—Arsenic Bases.—Compounds of Methyl with Metals.—Mothnno
and Substitution Products.
FORMYL CoMKioMns ... ... ... .. ... ... 108
Formnldeliydo.—Formic Aci«l.
ETHYL COMPOUNDS ... ... ... ... .. ... ... 107
Ethyl Alcohol. — Ethyl Cyanides. — Nitrogon Boson—Phosphorus
Bases.—Antimony Basra.—Bismuth Bases.—Compounds of Ethyl and
Sulphur.—Compounds of Ethyl with Solenium and Tellurium.—Com-
pounds of Ethyl with Metals.—Ethnno und Substitution Products.
ACETYL COMPOUNDS ... .. ... ... ... ,.. 184
AcoUldekydc.—Aortic Acfcl.—Substitution Products of Acotio Acid.—
Substitution Products of Aeetonitrile.
PROPJL QROWT ... ... ... ... ... ... ... 160
Bum Gnonf ... . ... ... ... ... ... 164
Ani'L on PENTTL Gnoc* ... .. ... ... ... ... 169
HRXTL GROUP ... .. ... .. ... .. ... 165
Hemt, GKOUP ... ... ... ... ... ... ... 108
OOTYL GWOUP ... ... ... ... ... 169
NoOTt GROUP ... ... ... ... ... ... ... 170
DECATYL Gnoor ... ... .. ... ... ... ... 170
HEKDECATYL GHOUV ... ... ... .. ... ... 171
CETVL GROUP ... ... ... ... ... .. ... 171
SOLID FATTY ACIDS .. ... ... ... .. ... 172
<
WAX AND BKBH' W.VX ... ... ... ... .. 174
COMPOUNDS OF DYAD RADICATS ' 176
DrA» Avoonoh RADICALS ... ... ... ... ... 175
HONOBAHIO A01D8 op TUB Sr.niEs C H^ O ... ... 179
n n 3
BiBAsro ACIDS ... ... ... ... ... ... ... 182
ETUEKB COMPOUNDS ... ... ... ... .. ... 184
Ethoue.—Phosphorus mid Araonic Bases of Ethcno.
ETIIIDRKE CowrousD8 ... ... ... ... ... ... 196
QLYCOVLYL COMPOUNDS ... ... ... .. .., ... 187
Glycollic Aoid —Glyeollic Ethcra.—Glycollic Amides.
OXALYI, COMPOUNDS ... ... ... .. ... .. 201
Osullc Acid.—Osaltttos.—Ethors of Oxalic Acid—Amides of Oxalic
Acid.-—Aldohydos of Oxnlio Acid.
PROPENE Coiivoo.Nns ... ... ... ... ... ... 206
lsoMEitiDiis OF PROPENE COMPOUNDS ... ... ... ... 207
LACTTL ConpooNDs ... ... ... ... ... ... 208
Lactic Acid.—Lactatcs —Ethcra of Lactic Acid — AmiM-a ofl.actic Acid.
CONTENTS. k
PAOB
COMPOUNDS OP DYAD
ETIIENE-LACTTL A»D MALONYL COMPOUNDS ... ... ... ... 213
BUTENB COMPOUNDS ... ... ... ... ... ... 216
Oxybutyric Aoid.
SccoiNTti, COMPOUNDS ... ... ... ... ... ... 218
Suceinic Aoid.—Amides of Suceinic Acid.—Substitution Products of,
Succiuic Aoid.—laosuocinic Acid.
MALIC ACID ... ... ... ... ... ... ... 223
Amides of Malic Acid.—Fnnmric Acid and Maletc Acid.
TAUTAWOACW ... .. ... .... ... ... ... 228
Dextrotattaric Acid.—Tartratos —Ethets of Tartnric Acid.—Raeemic
Acid and Levotarturic Acid.—Inactive Twrtaric Acid.
COMPOUNDS CONTAINING FWE ATOMS at CARBON ... ... ... 281
COMPOUNDS CONTAININO SIS AND IWRB ATOMS OF CAUBON ... ... 288
Leucio Acid and Louciue.
ACIDS OF TUB SEEIKS C H _ O ... ... ... ... ... 236
n fo a 4
CITBIO AOID ... ... ... 237
Citrates.—Aconitic Acid.
DBOXAUO AOID ... ... ... ... ... .. ... 240
Umo ACID ... ... ... ... ... •... ... 241
Unites.—Xanthine, Sitrcine, and Ouauiuo.—Cteatino aud Crealininc.—
Caffeine aud Theobromine.
COMPOUNDS OF TRIAD RADICALS 252
PnoFBNYl ALCOHOL OH OLYCEBIN ... ... ... ... ... 2S8
PTTOPBHYI. ETHEB8 OF T11E FATTY AO1D8 ... ... ... ... 257
ALIA'L COMPOUNDS ... ... ... ... ... ... ... 261
Ados OF THE SERIES C H _0 ... .. ... ... ... 286
o 2ll a s
TETRAD RADICAL8 AND THK1R COMPOUNDS 278
HvnnocAnBoNs OF TIIE SERIES C H _j ... ... .. ... 278
n 8n
EitYTirovrE ... ... .. ... ... ... ... 277
COMPOUNDS OF HEXAD RADICALS 278
IIAMNITE ... ... ... ... .. ... ... ... ^78
Dulcito.—Qucroite.—Uaumtic Aniil.—Saccharic Acid.^-Mudc Aciils,—
Pyromucio Acid.—Furfural.—Pyrrol.
CHELIDONIO AOID AND MKCONIO ACID ... ... ... ... 233
CABBO-HYDRAl'KS 284
8ACOIIAUOSE8 ... .. .. .. ... ... ... 286
Cane-sagar.™Synauthrose.—Milk-sugar.—Slolttosc—Mclijsitoso.—Jfycoso.
GUJCOSES ... ... ... 288
Dextrose—Lovulosc—Galactoso (Sorbin, lnositc, Emnlyll).
. ... ... ... ... ... ... 292
Starch. —Dextrin. —GuH»8.-~Iattlin. ~ Glywigwi.—Cellulose.— Tu>
nlctu.
FsaMRNTATloN ... ... ... ... ... ... 297
Viaoua Fertneutntiou.—Laotic Fonuontatiou.—Batyric Iftirraonta-
tion.—Mucio Fermentation.
b
x CONTENTS.
FAI1B
TKRPENES AND CAMPH0B8 298
OWi OF TURPENWNB ... ... ... ... ... ... 299
TERI'EHKS OP CITRUS 8PB01E8 ... ... ... ... ... 801
TEUPENES FROM OTIIKR 80DH0R8 ... ... ... ... 802
CAOUTCHOUC AND.GUTTA.PERCIIA ... ... ... ... ... 802
CAMPHORS ... ... ... ... ... ... ... ... 803
Common Camphor.—Bornoo Camphor Gcraniol.—Menthol.—Enca-
lyptol.—Patchouli Oil.
OXIDATION PRODUCTS OF CAMPHORS .. .. ... ... 806
.. (. ... ... 807
AROMATIC COMPOUNDS 308
COMPOUNDS WITH Six ATO»S OP CAMION ... ... ... ... 817
Benzone. —Substituted Bonzonos. —Aniline. — Auilide*. —Substituted
Anilines. — Diamidobonamw. —Triamidobonzenc. — Azobenzeno Com.
pounds.—Diazobcn/cno Compounds.—Phenol.-Nitrepheuols.—Amido-
phenols.— Haloid-snbstitntion Products of I'hcnol.—Dioxybcnzcncs.—
Trioiybenzonca.—Additivo Compounds
COMVOUNDS wrm SEVEN ATOMS OP CAKBOK ... ... ... ... 345
Toluene—Substituted Toluones.—AinidotolueiiM.—If onoxytolucncs.
—Dioxytoluencs.
BENZYL COMPOUNDS ... ... ... ... ... 354
BEHZOYL COMPOUNDS ... ... ... ... ... •• 857
Bonzoic Acid.—Substituted Uonzoic A rids.
OXYBBNZYL AND OXTBBN3OYL COMPOUNUS . .. ... 867
CoifPOTOiM wira EwnT ATOSW OF CARBOM . . ... ... ... 871
DlMRTHYLBRNZEXES .. ... .. ... ... ... 874
Mothyl'tolueno. —lsoxylonc.—Orthoxylene.—Xylcnols.
TOLVL AND TOI.UYL COMPOUNDS ... .. ... ... 87?
TOLYLENE COMPOUNDS . ... ... ... ... ... 878
Oxmum COMPOUNDS.
PHTHAUO ACIDS . .. ... .. .. ... 381
ETUYL-UBNZEHE ... ... - ... ... — 882
STYBOLTt. COMPOUNDS ... .. ... ... ... ... 882
ETBENTL-BENZGNE . . .. .. ... ... 384
KTUINYL-nBNZBNR ... ... ... .. ... .. 88JS
COMPOUNDS WITH NINE ATOSW OP CAMION ... ... 386
TWMbTHYt^DKNZKNK8 ... ... .. ... ... ... 388
Mositylono.—Psoudocumonc.—Acids derived from TrinicthyHon-
CTUO3.
BT»YL-nBT«Yl..BKNZBNB . ... ... ... ... 889
FROVTWlBNZ'RSiF! -. ... ... ... ... ... 390
CVHRHB OV. IsOPROPtLB'EKZKNB ... ... ... ... ... 390
AM.YL-BFA7,KNK ... ... ... .. "... ... 391
Chinyl Compounds.—Ciunamyl Compounds.—PhonyMactic Acids.
—Oxyphonyl.propionio Acids.—Oxyphonyl-acrylic Acids.
COMPOUNDS WITH TUN ATOMH OF CAHBON .. ... ... ... 398
TBTRAMBTnYt-BENZF.NK OR DtTUENE .. .. ... ... 398
DIMETHYL-ETHYL BENZENE ... ... . ... ... 399
CONTENTS. »
PJIO»
AROMATIC COMPOUNDS— {amtinued).
DlETBYL.BENZENE ... ... ... ... .•• • 399
MBTHTL-PKOPYL-BEMZKNE ... ... ... •• ... 399
CYMENB ... ... 399
Cymyl and Cuminyl Compounds.
J.8OBBTYI/-BENZKNE ... ... ... ... ... ... 402
BUTElTTL.BENZr.NB ... ... ... . ... ... 408
COMPOVNPS WITH ELEVEN ATOMS OF CARBON ... .. ... 402
A.myl>bon2one. —Dtethyl -booiylene.
COMPOUNDS WITH TWBLVK ATOM8 OP CARBON ... ... ... 408
Amyl-toluene.
irBttmo AOIB ... ... ... ... .. ... ... -408
ANILINE COLOURS ... ... ... ... ... ... ... 407
Rosaniline.
PHENOL COLOURS ... ... ... ... ... ... ... 411
COMPOUNDS CONTAINING TWO OR MORE AROMATIC NUCLEI
LINK.ED TOGETHER BY CARBON 414
DrpitEsm, ... ... ... ... ... ... ... 414
DsPUBHYl-METHAHE OR BBNZYVBBNBEHF. ... .. ... 417
PtlRNYL-TOLYVJlKTIIAKB OR BMMTL-rOHrENE .. ... ,.. 418
BENZYL-ETnYLB'ENZESB ... ... ... ... ... 419
DlTOLYL ... ... ... ... ... ... ... 419
DlBBNZYL OR DlPKENTMSTItAHB ... ... ... ... 419
SiiLBEHB, ToumEKE, OB Dll<BENYL-ETI»ENB ... ... ... 419
Tl)LANB, OR })lPnENYL>ETmNE ... .. ... ... ... 422
DKIE8rrei HETBAHE ... .. ... ... ... ,.. 423
TlrtFHBNYL-METHANB ... ... .. ... ... ... 423
BmiEfcrni-DlEWUtE ... ... ... ... . . ... 423
DlPHTHALYt. ... ... . . .. ... ... . . 423
.. . . ... ... .. ... 424
.. ... ... . . ... . . 424
... .. ... ... ... 425
INDIGO GROUP ... ... ... ... ... .. ... 425
NAJTIWUSNE Gn<nn> .. ... ... ... ... .. 429
NAPHTIIAIENB ... ... ... ... .. ... ... 429
Hydronaphthalenes.—Nuphthalono Chlorite.—Substituted Nnph-
thalcnos.—OxynaphthtiKnic?.—Mercurydi«fti»httiyl.—Methyl-liaplv.
thftlanc—Aconaphthouo.— Naphtlionitrilca.— Nuphthuloiio-carlionic
Acida.—Naphthyl-pUcnyl-motlianc—Diiinplttliyls.
Qnoup ... ... .. .. ... ... 440
... . ... .. ... 440
ANTHRACENE GKOUP .. .. ... ... ... .. 443
ANTHUACENE ... ... ... ... ... ., . 443
Hydroanthroconcs.—Chloriuo and Bromino Derivatives.—Nitro and
Atnido Compounds.— Authroooncsulphonic Aoids.—Anthraquiuono
or Oxyuutlimccno —Oxyantliro^iiinonea —Dioxyanthmnuinones.—
Trioxynutlinuittinones. — Totroxyanthraqniuoncs. — Hexoxyantlira-
quinone, or Ruflgallia Acid.—Dimethyl, anthracene.
xii C0STJBNT8.
PAGE
COMPOUNDS CONTAINING TWO OR MOEE AROMATIC NUCLEI
LINKED TOGETHEB BY CARBON—[continued).
PYBENB ... .. ... ... ... ... ... 454
CHRYSENB ... ... ... ... ... ... ... 456
RBTENB ... ... ... ... ... ... ... 459
IDIUALENE ... ... ... '... ... ... ... 466
ON TUG CONNECTION EXISTINO BETWEEN THE COLOUU AND MOLECULAR
CONSTITUTION OF THE CARBON COMPOUNDS ... ... ... 456
DESTBUCTIYE DISTILLATION ... ... ... ... ... 457
GLUCOS1DES 459
GUJCOSIDES OF THE AROMATIC Gtaovp ... ... ... ... 459
TANNW AOIDH ... ... ... ... ... ... ... 463
GLUCOSIDES YIELD1NO PRODUCT OF UNKNOWN CONSTITUTION ... 465
ANIMAL GurcoslDKS ... ... ... ... ... ... *87
ARTIFICIAL BASES FROM VARIOUS SOURCES 46*
BASES FROM ANIMAL OIL ... ... ... ... ... ... 407
BASKS CONTAINED IN COAL TAR ... ... ... ... .. 468
BASES FROU TUB DESTHUCTIVE DISTILLATION OF ALKALOIDS ... ... 469
NATURAL BASES OR ALKALOIDS 470
VOLATILE ALKALOIDS ... ... ... ... ... ... 470
ALKALOIDS OCOORUING in OPIUM ... ... ... .. ... 472
ALKALOIDS OCOURKIKO IN STUYCUNOS RPEOIES ... ... ... 476
AMMLOKDS OCCUBIIINO m CINCHONA BAHKS ... ... ... ... 477
ALKALOIDS OCCURRING IN CHELIDONIVM MA JUS .. ... ... 480
ALKALOIDS OCOUUBINO IN VEIUTRUM ... .. ... ... 480
ALKALOIDS OCCURRING \S BEIIBEIIW VUUJAUIS ... ... ... 480
BliBEBItlNB ... ... .. ... .. ... ... 481
PlPEMNB ... ... ... ... ... ... ... 481
SlNAPlNF. ... ... - .. 482
ATROPIME ... ... ••• ... ... ... ... 488
COOASHR 482
PllYSOSTlOJllSE OR EsKftlNK ... ... ... ... .., 488
HYOSCYAMINK ... ... ... ... ... .. ... 483
AcoNirrNE ... ... .. .. ... ... ... 484
COLOHICINE ... ... ... ... ... ,. ... 484
EMETINE ... ,.. •-. ... ... . ... 484
•RAR.MAMNE ... ... ••• .. ... ... ... iH
SOLANINE ... ... ... ... ... ... ... 484
COLOURING AND BITTER PRINCIPLES 485
COMPOUNDS CONTAINED IN BILE AND OTHER SECRETIONS ... 488
ALBUMINOIDS OR PROTEIDS 491
GELATIN AND CUONDRIN ... ... ... ... ... ... 496
SILK ... ... 496
FBIUIENTS ... ... ... ... ... ... ... ... 497
T HE CHEMISTRY OF T HE CARBON
COMPOUNDS.
INTRODUCTION.
CAKBON is one of the most widely distributed elements occurring on
our planet. la the free state it is found in two allotropic modifications,
as Graphite and as Diamond. In combination with oxygen, it occurs
as Carbm Dioxide, forming a small but normal and important con-
stituent of out atmosphere, whilst Carbonates are met with in all
geological formations, often in immense layers, sometimes forming
whole mountain chains.
Far more numerous and varying, however, are the carbon compounds
existing in the bodies of plants and animals, carbon being the most
characteristic and important constituent of all organisms. When any
organized structure is heated out of contact with air, carbon is left
behind in the form of porous, amorphous charcoal Animal and
vegetable substances are the chief sources from whioh other carbon
compounds are prepared, and the number of these is so great as to
to exceed the compounds of the other elements taken together: more-
over, new ones are being daily brought to light.
By far the largest proportion of the carbon compounds, and chiefly
those occurring ready formed, contain only a few elements; most of
them being formed by the union of oarbon with hydrogen and oxygen;
many also contain nitrogen; some only carbon, hydrogen, and nitrogen,
whilst others consist only of carbon and hydrogen.
The substances of which the bodies of plants and animals are built up,
as well as most of the compounds that can be obtained from these
by chemtoal changes, exhibit certain peculiarities, enabling us to
distinguish them easily from mineral bodies. Formerly chemists
believed that the cause of this difference was, that life was necessary
to their f ormaUo n, and that there existed an essential difference between
organic and inorganic bodies. Hence chemistry has been divided into
organic and inorganic chemistiy. At that time it was understood
V B