CONTENTS

Part I OPEN-CHAIN COMPOUNDS

Section 1 SATURATED COMPOUNDS

Chapter 1 HYDROCARBONS, ALCOHOLS, INORGANIC

ESTERS AND CARBOHYDRATES P a g e

HYDROCARBONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Methods of formation - Kolbe electrosynthesis. Halogenation.

ALCOHOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 By reduction of esters and carbonyl compounds - Sodium reduction of

es ters - Reduction of es ters , etc., with lithium aluminum hydride - Catalytic reduction of es ters to alcohols - Reduction of carbonyl com- pounds t o alcohols - Reduction of addition compounds of formaldehyde and ethylene - Meerwein-Ponndorff-Verley reduction - Butlerow's syn- thes is of tertiary alcohols.

Behavior and reactions of alcohols - Reaction with alkali metals - For- mation of urethanes and thiourethanes - Action of halogens.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . INORGANIC ESTERS 17 Alkyl halides - Halides by use of hydrogen halides - Chlorides by reac-

tion of hydrogen chloride with alcohols in the presence of zinc c h l e ride - Replacement of hydroxyl groups with halogens by use of halides of phosphorus and other halides - Halides by exchange reactions - Sulfuric e s t e r s - Chlorosulfonic e s t e r s - Sulfurous e s t e r s - Hypo- chlorous and perchloric e s t e r s - Nitric e s t e r s - Boric, arsenious and sal icylic es ters - Orthosilicoformic esters.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . MERCAPTANS 23

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CARBOHYDRATES 26 Methods employed for lengthening carbohydrate chain - Nef reaction -

Degradative methods - Zempl&n's method - Ruff's method - Other

xvii

xviii CONTENTS

PC methods of degradation. Lobry de Bruyn-van Ekenstein transformation- Conversion of a ldoses t o ke toses and v ice versa - Preparation of some of t he simpler sugars - Structure of carbohydrates - Dependence be- tween optical rotation and configuration - Hudson's lactone rule - Hudson's arnide rule - Freudenberg's rule of shifting of optical rotation - Tschugaeff's rule - Principle of optical superposition - Betrand's

rule - Orientation of t h e oxygen bridge. Ethers of carbohydrates - Complete etherification of carbohydrates -

Howarth's method - Purdie and Irvine's method - Freudenberg and Hixon's method - Trityl ethers of carbohydrates - Preparation of glu- cos ides from halogenoses, ace ta tes , etc. - Synthesis of di- and poly- saccharides - Acetals and ke t a l s of carbohydrates - Preparation of diacetoneglucose - Monoacetoneglucose - Diacetonemannose - Di- acetonegalactose - Res i s t ance of alkylidene and arylidene derivatives of carbohydrates t o chemical reagents - Mercaptals of carbohydrates.

Sugar anhydrides. Esters of carbohydrates. Halogen derivatives of carbohydrates. Thio sugars - Seleno sugars. Amino sugars. Hydrazones and osazones of carbohydrates. Oxidation of carbohydrates.

Reduction of carbohydrates and their derivatives - Glucals - Pseudo- glucals.

Chapter 2 ETHERS AND RELATED COMPOUNDS

ETHERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods of preparation - Williamson's reaction - Special methods. Peroxides. Chemical characteristics of ethers - Cleavage of alkyl e thers - Oxonium

compounds.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ALKYLENE OXIDES Methods of preparcttion - Formation from unsaturated compounds - For-

mation through condensation reactions (Erlenmeyer's or Darzen's re- action).

Reactions of a lky lme oxides - Reaction with halogen ac ids - Reaction with sodium bisulf i te - Reaction with ammonia and amines - Reaction with water and other hydroxy compounds - Other reactions - Isomeriza- tion of alkylene oxides.

CON TENT 1 THlOETH ERS AND RELATED COMPOUND

Methods of formation - Sulfonium Dial kyl selenides. Dialkyl tellurides.

Chapter 3 ALIPHATIC CARBONYL

FORMA-I-10

ALDEHYDES ................,..,. Formation by oxidation or dehydration of a1

hydric alcohols and keto alcohols, etc. to hydrogenation of alcohols - Oxidation of I

aldehyde synthes is - Aldehydes from olefi by cleavage of unsaturated heterocycles - merization of oxides - Aldehydes through c o l s - Other methods of preparation.

KETONES . . . . . . . . . . . . . . . . . . . . . . Formation by oxidation of secondary alcoh

dioxide - Oppenauer dehydrogenation of t ion of ketones from ac ids - Ketones fro metallic compounds - Ketones from orga tones by reaction of acid chlorides with methods of preparation.

THIOALDEHYDES AND THIOKETONES ....

Chapter 4 REACTIONS INVOLVING

COMPOUNDS: Pa!

REACTIONS INVOLVING CARBONYL COMPC Enolization. Polymerization of aldehydes.

Reaction with alkali bisulfites - Decompositic Hydroxy sulfonic acids.

Reaction with Hydrocyanic acid - Amino n i d and ketones.

Reaction with amino compounds - Schiff basea amine, hydrazines and semicarbazide - 1d carbonyl compound with Girard reagents , Mannich reaction - Ring formation throud Biginelli 's reaction - Schmidt reaction. '

1

Page Bruyn-van Ekenstein transformation -

vice versa - Preparation of some carbohydrates - Dependence be- ion - Hudson's lactone rule -

of shifting of optical rotation 1 superposition - Betrand's

e etherification of carbohydrates - Irvine's method - Freudenberg and carbohydrates - Preparation of glu- , etc. - Synthesis of di- and poly- of carbohydrates - Preparation of

ose - Diacetonemannose - Di- ylidene and arylidene derivatives s - Mercaptals of carbohydrates.

r derivatives - Glucals - Pseudo-

ELATED COMPOUNDS

. . . . . . . . . . . . . . . . . . . . . . . . . n's reaction - Special methods.

- Cleavage of alkyl ethers - Oxonium

.......................... on from unsaturated compounds - For- actions (Erlenmeyer's or Darzen's re-

action with halogen acids - Reaction ammonia and amines - Reaction s - Other reactions - Isomeriza

CONTENTS

. . . . . . . . . . . . . THIOETHERS AND R E L A T E D COMPOUNDS. Methods of formation - Sulfonium compounds - Alkyl disulfides. Dialkyl selenides.

! Dialkyl tellurides.

Chapter 3 ALIPHATIC CARBONYL COMPOUNDS:

FORMAT ION

xix

ALDEHYDES 100 I ........................................ Formation by oxidation or dehydration of alcohols - Oxidation of poly-

hydric alcohols and keto alcohols, etc. t o aldehydes - Catalytic de- hydrogenation of alcohols - Oxidation of methyl groups - Rosenmund aldehyde synthesis - Aldehydes from olefinic compounds - Aldehydes by cleavage of unsaturated heterocycles - Aldehydes through the iso- merization of oxides - Aldehydes through oxidative cleavage of gly- cols - Other methods of preparation.

KETONES .......................................... 118 Formation by oxidation of secondary alcohols - Oxidation with selenium

dioxide - Oppenauer dehydrogenation of secondary alcohols - Forma- tion of ketones from acids - Ketones from acid chlorides and organo- metallic compounds - Ketones from organocadmium compounds - Ke- tones by reaction of acid chlorides with sodiomalonic es ters - Other methods of preparation.

THIOALDEHY DES AND THIOKETONES . . . . . . . . . . . . . . . . . . . . . . 130

Chapter 4 REACTIONS INVOLVING CARBONY L

COMPOUNDS: Part 1

REACTIONS INVOLVING CARBONYL COMPOUNDS . . . . . . . . . . . . . 140 Enolization. Polymerization of aldehydes. Reaction with alkali bisulfites - Decomposition of bisulfite compounds-

Hydroxy sulfonic acids. Reaction with Hydrocyanic acid - Amino nitriles derived from aldehydes

and ketones. Reaction with amino cornpounds - Schiff bases - Reaction with hydroxyl-

amine, hydrazines and semicarbazide - Isolation and purification of carbonyl compound with Girard reagents - Wolff-Kishner reaction - Mannich reaction - Ring formation through the Mannich reaction - Biginelli's reaction - Schmidt reaction.

CON TENTS

page Cannizzaro reaction. a c i d s - Acids from cyc l ic e s t e r s and c Reformatsky's reaction. from n i t r i l es - Formation from organome Aldol condensation - Condensat ion of e s t e r s - Acyloin condensa t ion - l a n e o u s other methods.

Formation of =,@-unsaturated carbonyl compounds - Polymerizat ion of . . . . . . . . . . . . . . . . . . a ldo ls - Reduct ion of unsaturated aldehydes.

HYDROXY AClDS

Reduction of carbonyl compounds - Conversion t o ca rb ino ls - Reduct ion Chemical behavior of hydroxy acids.

1 Methods of formation - Frankland and Duppa

of amino ketones - Reduct ion of d ike tones - Pinacone formation - . . . . . . . . . . . . . . . . . Complete reduction of t h e carbonyl group - Clemmensen reduction - ALDEHYDE ACIDS

Peroxides of carbonyl compounds - Decarboxylation of aldehydes. KETO ACIDS. . . . . . . . . . . . . . . . . . . . . Methods of formation.

Chapter 5 Diketo ac ids . REACTIONS INVOLVING CARBONYL Behavior of ke to a c i d s - ~ e t o - e n 0 1 isomerisr

COMPOUNDS: P a r t 2 of a c e t o a c e t i c es te r .

AMINO ACIDS.. . . . . . . . . . . . . . . . . . . . . ACETALS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194 Methods of preparation.

Formation - U s e of orthoformic e s t e r s - U s e of o r thos i l i c ic e s t e r s - Behavior of amino ac ids . A c e t a l s of ketenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ACID ANHYDRIDES

MERCAPTALS 203 Methods of formation.

HYDRATES AND PEROXIDES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204 I Behavior of a c i d anhydrides - Hydrolysis of

. . . . . . . . . . . . . . . . . . . . . . . . . . OTHER ADDITIVE COMPOUNDS 205 DECARBOXYLATION AND DEGRADATION Formation of e s t e r s of t h e t y p e RCH(OCOR'),, - Reac t ion with a c y l

chlorides - Reac t ion with alkyl hal ides .

. . . . . . . . . . . . . . . . . . . . . REACTION WITH METHYLENE GROUPS 206 Perkin reaction. Cla i sen condensation. Knoevenagel t y p e condenscrtions - Replacement of reac t ive hydrogens

HALOGENATION O F CARBOXYLIC ACIDS

PERACIDS AND ACYL PEROXIDES. ....

Chapter 7 ALIPHATIC ESTERS-ESTER I

with organic rad ica l s - R e a c t i o n wi th ni t roso compounds - R e a c t i o n E S T E R S . . . . . . . . . . . . . . . . . . . . . . . . with nitric oxide and ni t rous acid. Formation - Direct ester i f icat ion of acids

REACTION WITH AROMATIC COMPOLINDS; MISCELLANEOUS OTHER E s t e r s from a c i d chlorides - Schotton-B REACTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235 t ion by u s e of inorganic a c i d halides -

Reaction with aromatic compounds - Lederer-Manasse reaction. E s t e r formation with aromatic ac ids - st Chloromethylation - ~ydroxymethyla t ion . t e r s by a lcoholys i s of n i t r i l es - Ester e Willgerodt reaction - P a s s e r i n i reaction. diazomethane - Preparat ion of esters Halogenation of carbonyl compounds- Replacement of oxygen i n carbonyl

groups with chlorine - Preparat ion of ring compounds from diketones.

Chapter 6 ALIPHATIC CARBOXYLIC AClDS

............... ACIDS WITH NO OTHER FUNCTIONAL GROUPS 257

Methods of formation - Conversion of a lcohols t o a c i d s - Oxidation of a ldehydes t o a c i d s - Oxidat ion of ke tones and olef in hydrocarbons t o

E s t e r s by oxidation of carbonyl compounds k e t o n e s - E s t e r s from substituted acetoa

Behavior of es te r s . Inner e s t e r s o r l a c t o n e s - y-Lactones - 0 t h

t i o n i n t h e aromatic ser ies . Hydrolysis of esters .

ESTER CONDENSATIONS ..........-.. Condensat ion of e s t e r s with other esters -

t r i l e s - E s t e r condensat ions with ketone

p a g e

of esters - Acyloin condensation - onyl compounds - Polymerization of

- Conversion to carbinols - Reduction diketones - Pinacone formation -

1 group - Clemmensen reduction - - Decarboxylation of aldehydes.

. . . . . . . . . . . . . . . . . . . . . . . . . . 194 esters - Use of orthosilicic es ters -

... . . . . . . . . . . . . . . . . . . . . . . . . 203

........................... 204 .......................... 205

..................... GROUPS 206

tion of ring compounds from diketones.

CARBOXYLIC ACIDS

of alcohols t o acids - Oxidation of

CON TENTS xxi

Page acids - Acids from cycl ic e s t e r s and carbon monoxide - Formation from nitriles - Formation from organometallic compounds - Miscel- laneous other methods.

HYDROXY ACIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263 Methods of formation - Frankland and Duppa's method. Chemical behavior of hydroxy acids.

ALDEHYDE ACIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266

KETO ACIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267 Methods of formation. Diketo acids. Behavior of keto acids - Keto-en01 isomerism - Characteristic reactions

of acetoacetic ester.

AMINO ACIDS.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275 Methods of preparation. Behavior of amino acids.

ACID ANHYDRIDES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291 Methods of formation. Behavior of acid anhydrides - Hydro1,ysis of ac id anhydrides.

DECARBOXYLATION AND DEGRADATION OF ACIDS. . . . . . . . . . . . 295

HALOGENATION OF CARBOXY L l C ACIDS . . . . . . . . . . . . . . . . . . . 299

. . . . . . . . . . . . . . . . . . . . . . . PERACIDS AND ACYL PEROXIDES. 302

Chapter 7 ALIPHATIC ESTERS-ESTER CONDENSATIONS

ESTERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311 Formation - Direct esterification of a c i d s - By vapor phase ca ta lys is -

Esters from acid chlorides - Schotton-Baumann reaction - Esterifica- tion by u s e of inorganic acid halides - Es te r s from acid anhydrides - Ester formation with aromatic ac ids - Es te r s from metallic s a l t s - Es- ters by alcoholysis of nitriles - Ester exchange - Ester formation with diazomethane - Preparation of e s t e r s from acetylenes and olefins - Esters by oxidation of carbonyl compounds and rearrangements of halo ketones - Es te r s from substi tuted acetoacetic e s t e r s - Orthoesters.

Behavior of esters. Inner esters or lactones - y-Lactones - Other lactones - Lactone forma-

tion in the aromatic series. Hydrolysis of esters.

ESTER CONDENSATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339 Condensation of e s t e r s with other e s t e r s - Ester condensation with ni-

tr i les - Ester condensations with ketones - Condensations with re-

xxii CONTENTS

Page active methylene in miscellaneous other compounds - Acyloin con- densation with aliphatic e s t e r s - Formation of glycidic e s t e r s - Be- havior of keto es ters - Alkylation of esters.

Chapter 8 ALIPHATIC AClD HALIDES, AMIDES AND

RELATED COMPOUNDS

ACID HALIDES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359 Methods of formation - Hydrolysis of acid chlorides. Syntheses involving the use of acid halides - Arndt-Eistert synthesis -

Halogenation of acid halides - Hell-Volhard-Zelinsky reaction.

ACID AMIDES AND RELATED COMPOUNDS . . . . . . . . . . . . . . . . . . 367 Methods of formation - Amides from acids and es ters - Amides from acid

chlorides and anhydrides - Amides from nitriles - Amides by other methods - The Beckrnann transformation.

Properties and behavior of amides - Hydrolysis of amides - Bouveault's method.

Miscellaneous reactions of amides - ~ofrnann 's reaction. Polypeptides - Degradation of peptides with hypobromous acid. Amide and imide chlorides. Thioamides and selenoamides.

AMINO COMPOUNDS RELATED TO ACID AMIDES . . . . . . . . . . . . . . 394 Acid hydroxides. Acid azides - Curtius degradation.

HYDROXAMIC ACIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401 Lossen rearrangement.

IMlNO ETHERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403 Thio imino ethers.

AMlDlNES.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405 Guanidines.

AMIDOXIMES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410

Chapter 9 ALIPHATIC NITRILES AND RELATED COMPOUNDS

NITRILES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420 Formation - Replacement of halogens and other acid radicals with cyano

group - Replacements involving other simultaneous changes - Replace- ment of sulfo and sulfonic groups - Nitriles from aromatic diazo com- pounds - Other methods of formation.

I Reactions of nitriles - Hydrolysis - Conv

with alcohols - Reaction with amines - t ion with halogens - Cyanogen halides ides - Cyanamides - Reactions of Cya 1 with Grignard reagents - Alkylation of ali Reduction - Polymerization -

' ISOCYANIC, THlOCYANlC AND ISOTHl ACID . . . . . . . . . . . . . . . . . . . . . . .

lsocyanic esters - Formation of ureas - F merization.

Thiocyanic and isothiocyanic esters-Form Other reactions.

Thiocyanation by means of thiocyanogh, %

Fulminic acid. I Chapter 104

ALIPHATIC AMINES AND REL

AMINES. . . . . . . . . . . . . . . . . . . . . . . . . Methods of formation - By replacement of

s i s - Replacement of hydroxyl groups amination of carbonyl compounds - Leuc amines through the reduction of nitro corn and nitriles - Other methods.

Imines. Carbodiimides. Quaternary ammonium compounds - Pyroly

compounds.

I Separation of amines - Properties of at amines - Acylation of amines.

I Degradative reactions - Hofmann's degr* bromide method - v. Braun's acylation me( actions.

Halogenation of amines. I

Stieglitz rearrangement.

I HYDRAZINES, HYDROXYLAMINES, PHOSPH Alkyl hydrazines. Alk y l h ydroxylamines - Trialkyl amine oxi& Phosphines. Arsines.

P a g e unds - Acyloin con-

Formation of glycidic e s t e r s - Be-

HALIDES, AMIDES AND

. . . . . . . . . . . . . . . . . . . . . . . . . . 359

halides - Arndt-Eistert synthesis - 1-Volhard-Zelinsky reaction.

. . . . . . . . . . . . . . . . . . POLINDS 367 m acids and esters - Amides from acid ides from nitriles - Amides by other

- Hydrolysis of amides - Bouveault's

ptides with hypobromous acid.

. . . . . . . . . . . . . . TO ACID AMIDES 394

. . . . . . . . . . . . . . . . . . . . ...... .'. 401

. . . . . . . . . . . . . . . . . . . . . . . . . . . 403

. . . . . . . . . . . . . . . . . . . . . . . . . . . 405

. . . . . . . . . . . . . . . . . . . . . . . . . . . 410

S AND RELATED COMPOUNDS

. . . . . . . . . . . . . . . . 420

and other acid radicals with cyano r simultaneous changes - Replace-

rom aromatic diazo com-

CONTENTS xxiii

page Reactions of nitriles - Hydrolysis - Conversion of t o amides - Reaction

with alcohols - Reaction with amines - Reaction with ac ids - Reac- tion with halogens - Cyanogen halides - Reactions of cyanogen hal- ides - Cyanamides - Reactions of Cyanamides - Reaction of nitriles with Grignard reagents - Alkylation of aliphatic nitriles - Cyclization - Reduction - Polymerization - Reactions of cyanuric chloride.

ISOCYANIC, THlOCYANlC AND ISOTHIOCYANIC ESTERS; FULMlNlC ACID . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446

lsocyanic esters - Formation of ureas - Formation of urethanes - Poly- merization.

Thiocyanic and isothiocyanic esters - Formation of ureas and thioureas- Other reactions.

Thiocyanation by means of thiocyanogen.

Fulminic acid.

Chapter 10 ALIPHATIC AMINES AND RELATED COMPOUNDS

AMlNES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465 Methods of formation - By replacement of halogens - Gabriel's synthe-

sis - Replacement of hydroxyl groups by amino groups - Reductive amination of carbonyl compounds - Leuckart reaction - Preparation of amines through the reduction of nitro compounds, azomethines, amides and nitriles - Other methods.

Imines. Carbodiimides., Quaternary ammonium compounds - Pyrolysis of quaternary ammonium

compounds.

Sepamtion of amines - Propert ies of amines - Characterization of amines - Acylation of amines.

Degradative reactions - Hofmann's degradation - v. Braun's cyanogen bromide method - v.Braun's acylation method - Other degradative re- actions.

Halogenation of amines.

t Stieglitz rearrangement.

i HYDRAZINES, HYDROXYLAMINES, PHOSPHINES AND ARSINES.. . . . 489 I

Alkyl hydrazines. Alkyl hydroxylamines - Trialkyl m i n e oxides. Phosphines. Arsines.

xxi v CONTENTS

page . . . . . . . . . . . . . . . . . . . . . . . . . . ALIPHATIC DIAZO COMPOUNDS 492

Preparation. Reactions of aliphatic diazo compounds. Reactions of hydrazoic acid.

Chapter 11 AL IPHATIC HALOGEN COMPOUNDS

. . . . . . . . . . . . . . . . . . . . . . ALIPHATIC HALOGEN COMPOUNDS.. 512 Methods of formation - Halogen exchange. Fluorination - Fowler's method - Simons process - Fluorination by re-

placement of halogens and amino or hydroxy groups - Miscellaneous other methods.

Properties of halogenated hydrocarbons - Isomerization - Reactivity of halogens in halo compounds - Reactivity ofhalogensin aromatic com- pounds - Reactivity of halogens in miscellaneous other compounds - Olefins from halo compounds - Replacement of halogens with various groups - Wurtz reaction - Catalytic removal of halogens with hydrogen.

Chapter 12 GRIGNARD REACTION

GRIGNARD REACTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 543 Preparation of organomagnesium compounds - Organomagnesium com-

pounds of acetylene and other compounds with reactive hydrogen - Evaluation of Grignard reagents - Qualitative t e s t for the detection of organomagnesium halides - Stability of Grignard reagents - Procedure in carrying out Grignard reaction - Reaction of Grignard reagents with carbonyl compounds - Olefin formation - Reaction with halo- and amino carbonyl compounds - Reaction with aldehyde and keto es ters - Reac- tion with unsaturated carbonyl compounds - Enolization induced by organomagnesium halides - Reaction with acetals - Reaction with es ters - Reaction with lactones - Reaction with unsaturated carboxylic es ters - Reaction with acid chlorides - Reaction with anhydrides - Reaction with carbon dioxide - Reaction with carbon monoxide - Re- action with carbon suboxide - Reaction with acid amides - Reaction with iminoethers - Reaction with acid azides - Reaction with nitriles - Reaction with cyanogen halides - Reaction with isonitriles, isocyan- ates, etc. - Reaction with ethers - Reaction with alkylene oxides - Reaction with hydrocarbons - Wurtz type reaction - Coupling induced by oxidative reactions - Reaction with ac ids and hydroxy and amino

CONTENT 1 compounds - Reducing effect of Grignard nard reagents - Reaction with nitrogen compounds of sulfur, selenium, with silicon compounds - and other elements.

FRIEDEL-CRAFTS

REACTIONS INVOLVING ALIPHA'I'IC HAL Preparation of aluminum chloride - Use of c

chloride - Position of entrance of alkyl gr during Friedel-Crafts reaction.

Condensations of benzene and its deriwtiv compounds - Reactions with naphthalene - compounds. 1

REACT IONS INVOLVING ACY L HALIDES Procedure - Position of attachment of acyl Reactions 04 benzene and its derivatives

halides - Reactions with halo acyl halid rated aliphatic acyl halides - Reactions and miscellaneous other aliphatic acyl chl matic acid chlorides.

Reactions with dibasic acid halides - Rea actions with oxalyl chloride - Reactions j actions with succinyl chloride and miscd acid chlorides.

Reactions with polynuclear compounds. React ion5 with heterocycl ic compounds.

REACTIONS INVOLVING ACID ANHYDRIDES Posit ion of entrance of acyl groups - Reactid

saturated dicarboxylic anhydrides - R e a d unsaturated dicarboxylic anhydrides - Req dride and other cyclic dicarboxylic anhydridq

REACTIONS WITH HALO COMPOUNDS OF S(, PHOSPHORUS AND ARSENIC .........

VARIANTS O F FRIEDEL- CRAFTS REACTlq Use of alkyl sulfates and other alkyl esters!

cohols - Reaction with unsaturated compod !

Page . . . . . . . . . . . . . . . . . . . . . . . . . . 492

. . . . . . . . . . . . . . . . . . . . . . S . . 512

rocess - Fluorinat ion by re- oxy groups - Miscel laneous

arbon$ - Isomerization - React ivi ty of Reactivity o fha logens in aromatic corn- s in miscellaneous other compounds - Replacement of halogens with various

ytic removal of halogens with hydrogen.

. . . . . . . . . . . . . . . . . . . . . . . . . . 543 compounds - Organomagnesium com- compounds with react ive hydrogen - - Qualitative t e s t for t h e detect ion of

e n t s - Procedure ard reagents with

n with halo- and amino with aldehyde and ke to e s t e r s - Reac-

at ion induced by t a l s - Reac t ion with nsaturated carboxylic

with anhydrides - Reaction with carbon monoxide - Re-

Reaction with ac id amides - Reac t ion h acid azides - React ion with n i t r i l es -

isoni t r i les , isocyan- hers - Reaction with alkylene ox ides - Wurtz type reaction - Coupling induced

ction with ac ids and hydroxy and amino

CONTENTS

xxv I Page

compounds - Reducing effect of Grignard r e a g e n t s - Oxidation of Grig- nard reagents - Reac t ion with nitrogen compounds - Reac t ion with compounds of sulfur, selenium, phosphorus, s i l icon, e tc . - Reac t ion with s i l i con compounds - Reac t ion with compounds of boron, scandium and other elements .

Chapter 13 FRIEDEL- CRAFTS REACTION

REACTIONS INVOLVING AL IPHATIC HALO COMPOUNDS. . . . . . . . . 623 Preparation of aluminum chloride - U s e of c a t a l y s t s other t h a n aluminum

chloride - P o s i t i o n of e n t r a n c e of a lkyl groups - Isomerizat ion induced during Friedel-Crafts reaction.

Condensations of benzene and its derivatives with various types of halo compounds - R e a c t i o n s with naphthalene - R e a c t i o n s with heterocycl ic compounds.

REACTIONS INVOLVING ACY L HALIDES . . . . . . . . . . . . . . . . . . . . 638 Procedure - P o s i t i o n of a t tachment of acy l groups. Reactions of benzene and its derivatives with various types of acyl

halides - R e a c t i o n s with h a l o a c y l h a l i d e s - R e a c t i o n s with unsatu- rated a l ipha t ic a c y l h a l i d e s - Reac t ions with ce r ta in aryl-substituted and misce l laneous other a l ipha t ic a c y l ch lor ides - Reac t ions with aro- matic a c i d chlorides.

Reactions with dibasic acid halides - Reac t ions with phosgene - Re- ac t ions with oxalyl chloride - R e a c t i o n s with malonyl chloride - Re- act ions with succ iny l chloride and misce l laneous other dicarboxylic acid chlorides.

Reactions with polynuclear compounds. Reactions with heterocyclic compounds.

. . . . . . . . . . . . . . . . . REACTIONS INVOLVING ACID ANHYDRIDES. 660 Pos i t ion of en t rance of a c y l groups - Reac t ions with s u c c i n i c and other

saturated dicarboxylic anhydrides - Reac t ions with maleic and other unsaturated dicarboxylic anhydrides - R e a c t i o n s with phthal ic anhy- dride a n d other c y c l i c dicarboxylic anhydrides.

REACTIONS WITH HALO COMPOUNDS OF SLILFUR, SELENIUM, PHOSPHORUS AND ARSENIC . . . . . . . . . . . . . . . . . . . . . . . . . . 670

VARIANTS OF FRIEDEL- CRAFTS REACTION. . . . . . . . . . . . . . . . . 673 Use of a lky l s u l f a t e s and other alkyl e s t e r s - Alkylation by u s e of al-

cohols - Reac t ion wi th unsaturated compounds - Zincke ' s method.

CONTENTS I CONTE NS I Chapter 14 . . . . . . . ALIPHATIC NITRO AND NITROSO COMPOUNDS, SULFONIC ORG ANOCADMIUM COMPOUNDS

AND SULFlNlC ACIDS, AND RELATED COMPOUNDS ORGANIC DERIVATIVES OF MERCURY . Page Direct reaction of mercury with alkyl halid

NITRO COMPOL~NDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685 Mercuration by means of mercuric oxide Preparation - Direct nitration of aliphatic compounds - Vapor phase ni- with unsaturated compounds - Mercury ac

tration - Replacement of halogens with nitro groups - Meyer's reac- actions of mercury alkyls - Mercuration tion - Kolbe's reaction - Nitro derivatives from unsaturated compounds mercuric aceta te - Mercuration with othe - Miscellaneous methods - Nitramines. placement of acid groups by mercury - Ne

Reactions of nitro compounds - Reaction with alkali hydroxides - Re- curation by means of Grignard reagents - actions involving alkali metal derivatives of nitroparaffins - Reaction actions of arylmercury compounds.

with ac ids - Reaction with aldehydes and ketones - Reaction with . . organomagnesium halides - Reduction of nitro compounds.

ORGANIC COMPOUNDS OF ALUMINUM.

. . . NITROSO COMPOUNDS 702 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF THALLIUM

. . OXIMES.. . . 703

ORGANIC COMPOUNDS OF GALLIUM.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... Preparation. ORGANIC COMPOUNDS OF INDIUM

...... Reactions of oximes. ', ORGANIC COMPOUNDS OF LEAD

SULFON~C ACIDS.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 707 ORGANIC COMPOUNDS OF TIN. ....... : Pleparation - Direct methods of sulfonation - Oxidation of thiols to sul- ORGANIC COMPOUNDS OF GERMANIUM. . ,

fonic ac ids - Replacement of halogens with the sulfonic group - Sul- .... fonic ac ids from olefins - Reed's reaction - Sulfonic ac ids by miscel-

ORGANIC COMPOUNDS OF BISMUTH i .. laneous reactions. ORGANIC COMPOUNDS OF CHROMIUM..

Reactions of sulfonic acids. FERROCENE . . . . . . . . . . . . . . . . . . . . .A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . SULFlNlC ACIDS 7171

Amides of oxyacids of sulfur. \ SULFONES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 718

Sulfones by oxidation of sulfides - From halo compounds - From sulfinic acids and aldehydes - From olefins and sulfur dioxide.

Reactions of sulfones. . . . . . . . . . . . . . . . . . . THIOSULFUR lC AND THlOSLlLFONlC ACIDS 724

Chapter 15 ORGAN0 METALLIC COMPOUNDS

. . . . . . . . . . . . . . . . ORGANIC DERIVATIVES OF ALKALI METALS. 733 Organosodium compounds. Organ01 ithium compounds.

. . . . . ORGANIC COMPOUNDS OF SILVER, GOLD AND PLATINUM.. 742

Chapter 16 ORGANIC COMPOUNDS OF N

METALLO IDS I ORGANIC COMPOUNDS OF BORON ......

Reactions of organo boron compounds.

ORGANIC COMPOUNDS OF SILICON.. .... Polysil icanes - Polysilicones - Silicon He

reactions of organic silieon compounds. I ORGANIC COMPOUNDS OF ARSENIC ...

Alkyl and aryl ars ines - Alkyl and aryl sonium compounds - Alkyl and aryl and sulfo ac ids - Bart's reaction - heterocycles - Properties and reactions o Estimation of arsinic acids.

MAGNESIUM DIALKYLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7431 ORGANIC COMPOUNDS OF ANTIMONY.. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ORGANOZINC COMPOUNDS 744 Alkyl and aryl st ibines - Bart type reaction

ORGANOBERYLLlUM COMPOUNDS.. . . . . . . . . . . . . . . . . . . . . . . . Properties and reactions of organic antimo

CON TE N 7s xxvii

Page

POUNDS, SULFONlC . . . . . . . . . . . . . . . . . . . . . . . . . . . ORGANOCADMIUM COMPOUNDS 746

$, AND RELATED COMPOUNDS ORGANIC DERIVATIVES OF MERCURY . . . . . . . . . . . . . . . . . . . . . 747 Direct reaction of mercury with alkyl halides - Alkyl mercury halides -

Mercuration by means of mercuric oxide - Reaction of mercury sa l t s . . . . . . . . . . . . . . . . . . . . . . . . . . . aliphatic compounds - Vapor phase ni- with unsaturated compounds - Mercury acetylides - Properties and re-

ens with nitro groups - Meyer's reac- actions of mercury alkyls - Mercuration of aromatic compounds with mercuric ace t a t e - Mercuration with other mercury compounds - Re- placement of ac id groups by mercury - Nesmejanow's synthesis - Mer-

Reaction with alkali hydroxides - Re- curation by means of Grignard reagents - Mercury heterocyles - Re- itroparaffins - Reaction actions of arylmercury compounds.

ydes and ketones - Reaction with ORGANIC COMPOUNDS OF ALUMINUM . . . . . . . . . . . . . . . . . . . . . . 758 ion of nitro compounds. . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF 'THALLIUM 759

702 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF GALLIUM 760 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 703 ORGANIC COMPOUNDS OF INDIUM . . . . . . . . . . . . . . . . . . . . . . . . 760

\ . . . . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF LEAD 761

. . . . . . . . . . . . . . . . . . . . . . . . . . 70 ORGANIC COMPOLlNDS OF TIN . . . . . . . . . . . . . . . . . . . . . . . . . . . 766 ulfonation - Oxidation of thiols t o sul- ORGANIC COMPOUNDS OF GERMANIUM. . . . . . . . . . . . . . . . . . . . . 772 &gens with the sulfonic group - Sul- . . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF BISMUTH 775 ss reaction - Sulfonic ac ids by miscel-

ORGANIC COMPOLINDS OF CHROMIUM . . . . . . . . . . . . . . . . . . . . . . 777

FERROCENE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717

Chapter 16 718 ORGANIC COMPOUNDS OF NON-METALS AND . . . . . . . . . . . . . . . . .

METALLOIDS fins and sulfur dioxide. . . . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF BORON 786

Reactions of organo boron compounds. . . . . . . . . . . . . . . . . . 724 . . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF SILICON. 787 Polysil icanes - Polysil icones - Silicon heterocycles - Properties and

reactions of organic si l icon compounds. METALLIC COMPOUNDS . . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF ARSENIC 790

. . . . . . . . . . . . . . . . ALKALI METALS. A1kyl and aryl arsines - Alkyl and aryl halo arsines - Quaternary ar- sonium compounds - Alkyl and aryl a rsenic oxides, acids, sulfides and sulfo ac ids - Bart's reaction - Bechamp's reaction - Arsenic heterocycles - Properties and reactions of organo arsenic compounds - . . . . . . . LVER, GOLD AND PLATINUM Estimation of arsinic acids.

........................... 743 . . . . . . . . . . . . . . . . . . . . . . ORGANIC COMPOUNDS OF ANTIMONY 804 . . . . . . . . . . . . . . . . . . . . . . . . . . . . Alkyl and aryl st ibines - Bart type reaction - Antimony heterocycles - N D S . . , , . , . . , . . , . . . , . . . . , , . . . Properties and reactions of organic antimonials.

CONTENTS

page

ORGANIC COMPOUNDS OF SELENIUM AND TELLURIUM . . . . . . . . . 809 Tellurium heterocycles.

ORGANIC COMPOUNDS OF PHOSPHORUS . . . . . . . . . . . . . . . . . . . . 812

Esters by replacement of halogen - Replacement of halogens with oxy- gen - Replacement of halogens with sulfur by use of Grignard reagents.

Preparation of phos~hines and related cornpounds - Phosphines by the Wurtz reaction - Phosphines from metallic phosphides - Phosphines by reaction of phosphorus trichloride with organic mercury compounds - Halogen exchange - Phosphines by Friedel-Crafts reaction - Phos- phines and their derivatives by addition of phosphorus halides t o unsat- urated compounds - Michaelis-Arbuzov reaction - Addition of com- pounds of type RX t o phosphines - Addition of halogens t o phosphines and related compounds - Addition t o carbonyl compounds - Replace- ment of halogens in phosphorus compounds with amino groups. Phos- phorus amides - Use of Schotten-Baumann reaction - Reaction of s a l t s of hypophosphorous acid with aromatic hydrazines - Reaction of hy- droxy compounds with phosphorus pentoxide and phosphorus pentasul- fide - Reaction of amines with phosphorus pentasulfide.

ERRATA

Page 11, line 21: for alcoxide read alkoxide ,Page 22, line 19: for coho1 read composition Page 26, side heading and lines 17 and 19: for set Page 53, line 24: for quire read quite Page 59, line 22: for galatonic read galactonic Page 79, line 7: for I-clycerol read 1-glycerol Page 85, line 10: for bulyrates read butyrates Page 87, line 18: for velicity read velocity Page 108, line 7: for lenic read linic Page 109, line 23: for dimerized read dimerizes Page 120. Line 23: for caid read acid Page 128, line 1: for acid read acids Page 201, line 8: for rnonixide read monoxide; 4th

read 2CH2 = C(OC2H5)2 Page 202, line 2: for minearl read mineral; line 23

panied by Page 212, line 21: for acetyl- read acetylenic Page 220, line 25: for p-nitrostlibene read pnitros Page 225, line 23: for sulvent read solvent Page 236, line 18: for pisition read position Page 248, line 2: for Monochloracetone read Monoc Page 269, line 15: for caralytically read catalytic1 Page 291, line 19: for phosphornolyodic read phosl Page 293, line 12: for substitutes read substituenl Page 300, line 23: for Tye read The; line 31: for1

read a-Rromoacetoacetic Page 301, line 16: for Hall-Volhard read Hell-Vob Page 3 17, line 3 under "Acid": for Chloracetic re Page 360, line 36: for Atropic acid read Atropic ac Page 368, line 7: for amide read imide; line 17: fo Page 392, line 19: for arnides read imides Page 394, line 3: for hydrazines reed hydrazides Page 420, line 10: for cyanhydrin read cyanohydrh Page 43.1, line 12: for end product of diaminotriazir

diaminotriezine, Page 438, line 1: for action read reaction Page 443, line 4: for ehereal read ethereal Page 445, line 20: for ester read esters Page 454, line 6: for hydroxyurea read hydroxyiso~ Page 474, line 17: for Beckam reed Beckmaw Page 482, line 4: for (C3H7)2NH.NN02 read (C3E Page 483, last line: for rnjxture read mixture Page 502, line 16: for acid read acids Page 515, line 25: for prolylene read propylene Page 519, line 18: for of read with