Catalytic Isomerization of Biomass‐Derived Aldoses: A Review
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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
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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