rappoport - crc handbook of tables for organic compound identification 3e (crc, 1967)

Third Edition Handbook of Tables for Organic Compound Identification Compiled by Zvi Rappoport, Ph.D... PREFACE The present volume is a revised and enlarged third edition of the book fo

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Printed in the United States 15 16 17 18 19 20

First Edition Tables for Identification of Organic Compounds

Compiled by Max Frankel, Ph.D

Saul Patai, Ph.D

Assisted by Albert Zikha, Ph.D

Robert Farkas-Kadmon

Second Edition Tables for Identification of Organic Compounds

Compiled by Max Frankel, Ph.D

Saul Patai, Ph.D

Assisted by Albert Zilkha, Ph.D

Zvi Rappoport, Ph.D

Robert Farkas-Kadmon

64 by THE CHEMICAL RUBBER CO

Third Edition Handbook of Tables for Organic Compound Identification

Compiled by Zvi Rappoport, Ph.D

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PREFACE

The present volume is a revised and enlarged third edition of the book formerly titled TABLES FOR IDENTIFICATION O F ORGANIC COMPOUNDS, Four new classes of com- pounds, i.e., sulfonyl chlorides, sulfonamides, thiols and thioethers were added, bringing the number of classes included in the book to twenty-six The tables of alkanes, alkenes, alkynes, aromatic hydrocarbons, phenols, nitriles and sulfonic acids were all thoroughly revised and considerably enlarged In all, the addition of 2400 compounds

to the third edition, raised the total number of parent compounds in the book to over

8150

Three tables containing the dissociation constants o f more than 1050 phenols, organic acids and organic bases were added Correlation charts for I.R., Far I.R and N.M.R were also included

Explanatory sections entitled "Explanations and References" precede the tables In these sections the formulas of the derivatives and the full reaction equations for their preparation by the most important methods, together with some essential details and references to their preparations, are given

An index covering both the names and synonyms of the compounds was added at the end of the book An index listing the names of all tables and major subjects was also added

The main objective of this book is to assist chemists in the identification of organic compounds The organization of the compounds in classes according t o increasing boiling points should also assist in the search for standard vapor phase chromatography work For further information of techniques of organic analysis one or more of the following books should be consulted:

N D Cheronis, J B Entrikin and E M Hodnett, Semimicro Qualitative Organic Analysis, 3rd Ed., Interscience Publishers, New York, 1965

L Meites, Handbook of Analytical Chemistry, McGraw Hill Book Co., 1963

F Feigl, Spot Tests in Organic Analysis, 6th Ed., Elsevier Publishing Co., 1960

A I Vogel, A Textbook of Practical Organic Chemistry, 3rd Ed., Longmans Green and

The publication of the third edition would not have been possible without the work

of those involved in the preparation of the earlier editions The editor is thankful for the

part in the earlier work contributed by Professors M Frankel, S Patai and A Zilkha, and

the late Mr R Farkas-Kadmon Thanks are due also to Mrs E Shohamy and Mr A Glazer for assisting in collection of new data, t o Mrs Y Elmaleh for typing the index, and especially to Prof S Patai, who as consulting editor, read all the new material and gave many helpful suggestions The cooperation o f Dr Robert C Weast and Mrs F Thomas in the publication of the book is gratefully acknowledged

z

Contents

Abbreviations Explanations and References to the Tables Alkanes and Cycloalkanes

Gases, Liquids, Solids Alkenes, Cycloalkenes, Dienes and Polyenes Liquids, Solids

Alkynes (Acetylenes) Liquids, Solids Aromatic Hydrocarbons Liquids, Solids Halides

A) Alkyl and cycloalkyl halides

1 Chlorides, Liquids and Solids

2 Bromides, Liquids and Solids

3 Iodides Liquids and Solids B) Dihalides and polyhdhdes (non-aromatic)

1 Fluondes

2 Chlorides, Liquids and Solids

3 Bromides, Liquids and Solids

4 Iodides, Liquids and Solids

C) Aryl halides

1 Fluorides, Liquids

2 Chlorides, Liquids and Solids

3 Bromides, Liquids and Solids

4 Iodides, Liquids and Solids Aicohols

Liquids, Solids Phenols

Liquids, Solids Ethers

Liquids, Solids Aldehydes

Liquids, Solids Ketones

Quinones Carboxylic Acids Liquids, Solids AcyI Halides Acid Fluondes AcyI Bromides, Liquids, Solids AcyI Chlorides, Liquids Solids Acyl Iodides, Liquids, Solids Acid Anhydrides

Liquids, Solids Amides and Imides Liquids, Solids Esters

Liquids, Solids

Contents (Continued)

Ammo Acids Amines Primary and Secondary Amines Tertiary Amines

Liquids, Solids Carbohydrates Liquids, Solids Nitro Compounds Liquids Solids Nitriles

Liquids, Solids Sulfonic Acids Sulfonyl Chlorides Sulfonamides and Sulfonanilides Thiols (Mercaptans)

Thioethers (Sulfides) Acid Dissociation Constants of Organic Acids in Aqueous Solution

Acid Dissociation Constants of Phenols in Aqueous Solution

Dissociation Constants of Organic Bases in Aqueous Solution

1.R.-Infra-red Correlations Charts Far 1.R.-Far Infra-red Vibrational Frequency Correlation Charts

NMR-Characteristic N M R Spectral Positions for Hydrogen in Organic Structures

Miscibility of Organic Solvent Pairs Emergent Stem Correction for Liquid-in-Glass Thermometers

Correction of Boiling Points to Standard Pressure Molecular Elevation of the Boiling Point

Molecular Depression of the Freezing Point Carbohydrates

Fats and Oils Waxes Diamagnetic Susceptibilities of Organic Compounds Four-Place Logarithms

Periodic Table o f the Elements Table of Atomic Weights Index of Organic Compounds Index listing names of tables and major subjects Request for New Data

LIST OF ABBREVIATIONS USED

aboutacetic acidacetic anhydrideacetoneadditionalcoholalkaliamorphousanhydrousaromaticaqueousasymmetricblueblackboilingboiling pointbrownbenzenebrightbrownishcoldaboutcausticchloroformchlorobenzenecolorlesscompoundconcentratedcorrectedcrystalsdecomposesdextrorotatory(or D-configuration)derivative

deliquescentdilutedistillatedark

L racemic

efflorescentethylethyl acetateetherexplodesfromflakesfluorescentfreezing pointfreezes

um

;Iac'lit

?lycgrangrn,htnghyd

hyg , hygr

;iignmsol

1 , L

leaf Iflg 'grhqIngIt Ivs/Ti-

me , methmicrmixtmlmodmonohydmonocl

m p , M Pneed , nd

0-olor ord orgorthoxid

P-papartpetpet ethph

ph hydrazPhNO2plpowd

fumingglacialglitteringglycerolgranulargreenhotheatinghydrate orhydrolyseshygroscopicinactiveinsolubleignitesinsolublelevorotatory(or L-configura-tion)

leafletslargeligroinliquidlonglightleavesmctsmethylmicroscopicmixturemillilitermodificationmonohydratemonochnicmelting pointneedlesorthooliveorangeordinaryorganicorthorhombicoxidationparapalepartlypetroleumpetroleum etherphenylphenyl hydrazinenitrobenzeneplatespowder

prpurppyrrac

reelrecrredshrhombr

r hssecscar

s hshsisldslendsmsoftsol , solnsolvststabsubl

sym

tab , tabl

ten

tetrtoltransthktncltrimunsunstvacVvarvic-

V1SC

volatvltwwhyelyelsh, ylsh

>

<

ooxyl

prismspurplepyndineracemic(or racemate)rectangularrecrystallizationreddishrhombicrapidrapid heatingsolublesecondaryscarcelyslow heatingshortslightlysolidslender

fm o i l

smallsoftenssolution(s)solvent(s)steelstablesublimessymmetricaltablet(s), tablestertiarytetragonaltoluenetransparentthicktnchmctnmencunsymmetricalunstablevacuum, in vacuovery

variablevicinalviscousvolatile or volatilizesviolet

waterwhiteyellowyellowishabove, greater thanbelow, smaller thanirascible

xylene

EXPLANATIONS AND REFERENCES TO THE TABLES

The following section gives explanations and references for the preparation of the derivatives ing in the Tables Formulas of the derivatives as well as the mam methods for their preparation are givenUsually, only the reagents and the solvents required for the preparation of a derivative are mentioned withoutspecific details for the reaction conditions and the exact procedure The aim of these notes is mainly to enablethe worker to choose the method preferable in the conditions and the reagents available to him in his labora-tory for the denvatization of his specific compound However, THIS IS ONLY A REFERENCE SECTIONAND NOT AN INSTRUCTION M A N U A L AND THE QUOTED REFERENCES SHOULD BE CON-SULTED FOR THE ACTUAL PREPARATION OF DERIVATIVES, ESPECIALLY REGARDINGSAFETY HAZARDS INVOLVED IN THE WORK

appear-References are usually given for the preparation of all the derivatives having separate columns in the Tables,

as well as for important ones listed in the "miscellaneous" section of the Tables References to five differentpopular analytical textbooks are given, assuming that at least one of them, or another equivalent publication,would be available to the worker These are

N D Cheroms, J B Entnkin and E M Hodnett, Semimicro Qualitative Organic Analysis, 3rd edition,

Interscience, New York, 1965, quoted in the text as "Cheroms "

R P Linstead and B C L Weedon, A Guide to Qualitative Organic Chemical Analysis, Butterworth

Scien-tific Publication, London, 1956, quoted in the text as "Linstead "

R L Shnner, R C Fuson and D Y Curtin, The Systematic Identification of Organic Compounds, 4th

edition, John Wiley and Sons, New York, 1956, quoted in the text as "Shnner "

A I Vogel, A Textbook of Practical Organic Chemistry, 3rd edition, Longmans, Green and Co , London,

1957, quoted in the text as "Vogel "

F Wild, Characterization of Organic Compounds, 2nd edition, Cambridge University Press, Cambridge,

1958, quoted in the text as "Wild "

In addition, leading references from the original literature are also given Although the literature age is not complete (especially for the common derivatives) it was attempted to describe different methods, and

cover-to give as many references as possible cover-to less common derivatives having limited scope More references can

be found in the textbooks mentioned aboveDerivatives appear either in a separate column or in the "miscellaneous" section in the Tables, whereseparate columns are usually given for derivatives which should be tried first, and for which enough data areavailable Derivatives which should be tried as a second choice, or preferred derivatives for which not enoughdata are available appear in the "miscellaneous" section The explanations and the references for the differentderivatives are arranged usually in the same order as in the Tables Occasionally, this order is changed in theexplanatory notes in order to describe the derivatives in a logical order ( e g , in Table 17 the phenylurethaneappears in a separate column, while the phenylhydantom appears in the "miscellaneous" section in the "ex-planations and references" section the phenylhydantom appears directly after the phenylurethane)

Derivatives which are followed by an asterisk are those recommended for first trial Other derivativesshould be tried after these

Although "Ar" usually stands for monovalent aromatic group, we used it a few times in the following tions as a polyvalent aromatic residue This was done only for demonstration purposes

sec-EXPLANATIONS AND REFERENCES TO TABLE I

As a result of their inertness no general suitable derivative exists for alkanes and cycloalkanes terization is based only on the physical constants given in the Table melting and boiling points, index of re- fraction and density Any laboratory text-book will give adequate directions for the determination of these con- stants

Charac-EXPLANATIONS AND REFERENCES TO TABLE I

As a result of their inertness no general suitable derivative exists for alkanes and cycloalkanes terization is based only on the physical constants given in the Table melting and boiling points, index of re- fraction and density Any laboratory text-book will give adequate directions for the determination of these con- stants

Charac-T A B L E I A L K A N E S A N D C Y C L O A L K A N E S a) Gases and Liquids (Listed in order of increasing b.p.*)**

point, ¡

- 161 49

- 88 63 -42 07

'Derivative data given in order m p ,crystal color, solvent from which crystallized

**T = triple point, S = at saturation pressure

T A B L E I A L K A N E S A N D C Y C L O A L K A N E S a) Gases and Liquids (Listed in order of increasing b.p.* ) (Continued)

crystal color, solvent from which crystallized

Melting point, ¡

T A B L E I A L K A N E S A N D C Y C L O A L K A N E S

a ) Gases and Liquids (Listed in order of increasing b.p.* ) (Continued)

Name 3,6-Dimethyloctane

Melting point, "C

'Derivative data given i n order m p crystal color solvent from which crystallized

'Derivative data given i n order m p ,crystal color, solvent from which crystallized

T A B L E I A L K A N E S A N D C Y C L O A L K A N E S

b ) Solids (Listed in order of increasing m.p.*)**

N o Name

I

2

Pentadecylcyclopentane

n-Hexadecane (Cetane)

3 4 5 Tridecylcydohexane

Hexadecylcyclopentane

n-Heptadecane 6 7 8 Tetradecylcyclohexane

Heptadecylcyclopentane

n-Octadecane

9 10 11 Pentadecylcydohexane

Octadecylcyclopenlane

n-Nonadecane

12 13 14 Hexadecylcyclohexane

Nonadecylcyclopentane

n-Eicosane

15 16 17 Heptadecylcyclohexane

Eicosylcyclopentane

n-Heneicosane

18 19 20 Ortadecylcyclohexaiw

Heneicosylcyclopentane

n-Docosane

2 1 22 23 27 Tetracosylcyclopentane

28 Heneicosylcyclohexane

29 n-Pentacosane I

Docosylcydopentane

Nonadecylcydohexane

n.Tricosane

24 25 26 Eicosylcyclokxane

Tricosylcydopentane

n-Tetracosane

30 3 1 32 33 34 Pentacosylcydopentane

Docosylcyclohexane

Hexacosylcyclopentane

Nortricyclene (Tricyclo[2.2.1 Oa6]heptane)

n-Hexacosane

35 36 37 38 Melting point ¡ Cyclohexadecane

Tricosylcyclobexane

Heptacosylcydopentane n-Heptacosane

39 40 41 42 Boiling point "C

Tetracosylcydohexane

Cyclopentadecane Octacosylcyclopentane

n-octacosane

*Derivative data given i n order: m.p., crystal color solvent from which crystallized

**U = undercooled liquid

-

T A B L E I A L K A N E S A N D C Y C L O A L K A N E S b) Solids (Listed in order of increasing m.p.*)** (Continued)

Boiling point, " C

*Derivative data given i n order m p ,crystal color, solvent f r o m which crystallized

**U = undercooled l i q u i d

EXPLANATIONS AND REFERENCES TO TABLE II

Bromine addition compound *

Bromine additioncompoundFrom the alkene and bromine in carbon tetrachloride.

For directions and examples see: Cheronis, p 576; Shriner, p 106.

From the alkene and bromine in water.

See: Vogel, p 241.

From the alkene and bromine in chloroform.

See: C G Schmitt and C E Boord, / Amer Chem Soc., 54, 751 (1932).

2,4-Dinitrobenzenesulfenyl chloride addition compound *

NO2

2,4-Dinitrobenzenesulfenylchloride adduct

From the alkene and 2,4-dinitrobenzenesulfenyl chloride in glacial acetic acid.

For directions and examples see: Cheronis, p 577; N Kharasch and C M Buess, J Amer Chem Soc.,

71,2724(1949); D J Cram, J Amer Chem Soc., 71, 3883 (1949); N Kharasch, C M Buess and S I shun, J Amer Chem Soc., 74, 3422 (1952).

Stra-From the alkene and 2,4-dinitrobenzenesulfenyl chloride in benzene or in carbon tetrachloride.

See: N Kharasch and C M Buess, / Amer Chem Soc., 71, 2724 (1949).

From the alkene, mercaptosuccinic acid and benzoyl peroxide in methanol.

For directions and examples see: J G Hendrickson and L F Hatch, / Org Chem., 25, 1747(1960) Maleic anhydride adduct (from dienesj.

CHR

CH CH-CO^ CH CH-CO

^Maleic anhydrideadductFrom the diene and maleic anhydride in benzene.

For directions and examples see: Linstead, p 5 1 ; Vogel, p 943.

From the diene and maleic anhydride in xylene.

See: Linstead, p 51.

For general references see: M C Kloetzel in Organic Reactions, Vol 4 (Ed R Adams), John Wiley and

Sons, New York, 1948, p 1; H L Holmes in Organic Reactions, Vol 4, (Ed R Adams), John Wiley and Sons,

New York, 1948, p 60; O Diels and K Alder, Chem Ber., 62, 2081 (1929).

Nitrosochloride addition compound.

RCH=CHR' + NOC1 — • RCH(NO)CHC1R'

Nitrosochlorideadduct

•Derivatives recommended for first trial

WARNING: This is not an instruction manual References should be consulted for the preparation of derivatives

Handbook of tables for Organic Compound Identification, © 1967 CRC

E X P L A N A T I O N S A N D REFERENCES T O T A B L E I1 (Continued) From the alkene and nitrosyl chloride (prepared from sodium nitrite in concentrated hydrochloric acid)

in ether-acetic acid mixture

For directions and examples see: Linstead, p 52; R Perrot, Compt Rend., 203,329 (1936)

From the alkene and nitrosyl chloride (prepared from thionyl chloride and nitrogen trioxide) in ether

See: M Tuot, Compt Rend., 204,697 (1937)

'Derivatives recommended for first trial

- 133 77

-85

-88 9

-1152 -87 47

- 140 82

dl- dl- tetra- d/-

dl-

tetra- di- dt- tetra- di- tetra di-

dl-

dl- tetra-

Bromine addition product

> 83 -55 5

86 7 4-Dinitrophenyl- sulfenyl chloride,

7 7 5 8 5

Aercdptosuccinic acid adduct

1073 6 4ercaptosuccinic acid adduct,

122 3- 6 taleic anh adduct,

litrosochlor~de, 74

Mercaptosuccinic acid adduct,

153 7-4 0

limer 32, Maleic anh adduct, 164

5 Benzoquinone adduct, 75 6 laleic anh adduct,

61, pet eth , Oxid

by KMnO, -

HCOOH +

CH,COOH

*Derivative data given in order m p ,crystal color, solvent from which crystallized

**T = triple point, S = at saturation pressure

- 139 82

-131 53

- 137 82

-11343 -135 7

- 134 84

- 132 97

-76 01 -141 14

-138 45

K Bromc

- dl-

A

A-

A- 'etra-

ll- tetra- /I-

142 8 3 1 Pseudo- nitrosite 69 70 Perbenzoic acid oxid -epoxy- cyclopentane

b p 102 3

M ~ ~ c ~ ~ ~ o s u c c ~ ~ I I c dcid ddduct

1026 9

311 HNO, - suc- cinic ac 185 2,4-Dinitrophenyl- sulfenyl chloride

61 2 Mercapto- succinic acid ad- duct 94 5 5 7

i4ercaptosucciTiic acid adduct,

T A B L E 11 O R G A N I C D E R I V A T I V E S O F A L K E N E S , C Y C L O A L K E N E S ,

Boiling point,

Melting point,

kexa-

1.5-dl- tetra-

il-

tetra-

2 forms

1,trans-

2 c ~ - 3 , trans-4,

92 0

Melting point

-

di-

di- di- di-

d ~ - di-

di -

di-

dl -

dl- dl- dl-

dl -

di- 1.2-d~- dl-

I 5, K M n 0 , oxid - adipic ac ,

154,2,4-Dinitro- phenylsulfenyl chloride, 1 17 8

H B r - cyclo- hexyl bromide,

b p 165

klercaptosuccinic acid adduct

103 4- 9

*Derivative data given i n order m p ,crystal color, solvent from which crystallized

11-

il -

ll- ll-

fl- ll-

11-

11-

!,%dl- tetra-

O C

Bromine addition product

Miscellaneous

:educes Tollen's reagent on warm- ins

,4-Dinitrophenyl- sulfenyl chloride,

139 40

*Derivative data given i n order m p ,crystal color, solvent from which crystallized

T A B L E 11 O R G A N I C D E R I V A T I V E S O F A L K E N E S , C Y C L O A L K E N E S ,

Name

Boiling point

-87 38 olid at -80, l i q

wlaleic anh adduct,

104 2-5 0 CC1

wlercaptosuccinic acid adduct,

101 9-2 7

Mercaptosuccin~c acid adduct,

96 1- 6

*Derivative data given i n order m p ,crystal color, solvent from which crystallized

-c

D I E N E S A N D P O L Y E N E S

a ) Liquids 1 ) (Listed in order of increasing b.p.)* (Continued)

Melting point

'Derivative data given i n order m p crystal color solvent from which crystallized

Bromine addition product

59 5 70 eth

01

42 3 acet

Miscellaneous

H, - Cyclo heptane b p

1 8 20

Viercaptosuccinic acid adduct

1429 3 5

Mitrosochloride

83 4 Mitrosochloride

I 8 9

I B r - Dihydro bromide b p

109 I I

)xid i n air -poly meric peroxide 59

TABLE 11 ORGANIC DERIVATIVES OF ALKENES, CYCLOALKENES,

12 5-3 5

t3-5'34 t3 8-

t 5"'

(4-6 14-6,

14 6"

14-6

D I E N E S A N D P O L Y E N E S a) Liquids 1) (Listed in order of increasing b.p.)* (Continued)

- Melting

bichloride 88 9, Nilrosdle, 21 bd ,

141, dl Acrylic ac ddducl 1 12 3, lgr AgNO, ddduct,

173 4

litrosochloride,

134

Br, - Bromocyclo- octene, b p 7-8"

n2,? 1 5182, Di- chloride, b p

130 4-0 6%'>, m p -5, n? 1 5061,

D'? 1 1620

*Derivative data given in order m p ,crystal color, solvent from which crystallized

O C

D I E N E S A N D P O L Y E N E S

a ) Liquids 1 ) (Listed in order of increasing b.p.)* (Continued)

Melting point,

Nitrosochloride,

133 4 et ac

N-Bromosuccini- mide - bromo- cyclooctadiene,

Sitrosochloride,

1 14, acet

*Derivative data given in order m p ,crystal color, solvent from which crystallized

TABLE 11 ORGANIC DERIVATIVES O F ALKENES CYCLOALKENES,

6 3 5 4 5 64-7,

D."

x Bromo

I 8600 di-

I 823O 17802"

Bromine addition product

Miscellaneous

itrosochloride,

109, Hydro- bromide, 89, Nitrosobromide,

ercaptosuccinic ,cid adduct, '3 5- 8

'Derivative data given in order rn p ,crystal color, solvent from which crystallized

Miscellaneous

Nitrosochloride, 101-3

Dihydrochloride, 53-4, me al , Di- hydrobromide,

58 9, me al Di- hydroiodide, 76,

me al , Nitrosite,

155, Maleic anh adduct, 62.66-7

Nitrosite a 120-1,

8 105 6 [ale +49 I Nitro- site, a 11 3-4.8

105 Maleic anh adduct, 126-7, pet eth

Dihydrochloride,

72, Nitrosochio- ride, 106-7 Nitrosochloride, 100-4,2,4-Dinitro- phenylsulfenyl chloride, 195-6 Dihydrochloride,

71 5,me al [ a ] g -68 2, Di- hydrochloride, 72 Dihydrochloride, 50-l,al

[ a ] ~ +17 5

[a]i>5 +36, Nitro- sochlor~de 1 11, Nitrosate, H6d ,

ac a -me dl

*Derivative data given in order m p ,crystal color, solvent from which crystallized

O C

D I E N E S A N D P O L Y E N E S

a ) Liquids 1 ) (Listed in order of increasing b.p.)* (Continued)

Melting point,

O C

-49 19

-35 23 -23 07 -12 85

- 3 73

1 2

1 2 -2 5

A-

A- A-

Bromine addition product

Miscellaneous

Nitrosite, 155, me

al or chl , Maleic anh adduct, 205 8 Maleic anh adduct,

182

0, - Sebacic acid,

134 5

Mercaptosuccinic acid adduct,

1040 8

1% Hot KMnO -

n pentadecylic ac ,

52 3, Mercapto- succinic acid ad- duct, 105 0 8

Derivative data given in order m p ,crystal color, solvent from which crystallized

Miscellaneous

Maleic anh adduct, 143 4

0, - Sebacic acid, 134 5 Phenylazide adduct, 97 8 8 2

Nitrosochloride, 109- 10, Nitrosate, 210d Maleic anh adduct, 184 5-5 5, bz -I@, AgN03 adduct, 142 5 4 5, al

Maleic anh adduct, 97 8 5, bz -cyclohexane, AgNOa adduct, 124-5 5, al

A-

t.3-trans di-

121 2, Hydrochlo- ride, 125-7

'Derivative data given in order m p , crystal color, solvent from which crystallized

S = Supercooled liquid at 20Â

EXPLANATIONS AND REFERENCES TO TABLE III

Hg salt (Mercuric acetylide) *

Mercuric saltFrom the terminal alkyne and K2HgI4 (prepared from mercuric chloride, potassium iodide_aira potassium hydroxide)

For directions and examples see Linstead, p 52, J R Johnson and W L McEwen, J Amer Chem Soc,

48,469(1926)

Hydration to form carbonyl compound

For directions and examples see J G Sharefkm and E M Boghosian, Anal Chem , 33,640(1961)

From the alkyne, mercuric sulfate and sulfunc acid in 70% methanol, m 70% acetone or in 60% acetic acid

See Cheroms, p 576, H Erdmann and F Kother, Z Anorg Chem , 18, 48 (1898), R J Thomas, K N

Campbell and G F Henmon,/ Amer Chem Soc , 60,718 (1938)

From the alkyne, mercuric oxide and sulfunc acid in alcohol

See i R Johnson, A M Schwartz and T L Jacobs, J Amer Chem Soc , 60,1882(1938) NOTE For directions and examples for the preparation of the semicarbazones and the 2,4-dimtrophenyl-

hydrazones of the formed carbonyl compounds see explanations and references to Table IX and X, p 141, 142,

143

'Derivatives recommended for first trial

Handbook of tables for Organic Compound Identification, © 1967 CRC

-84 0 (sat press )

31 5744

-

a ) Liquids (Listed in order of increasing b.p.)*

Melting point, "C

Hydration product (RC=CR' - RC0CH.R J

and its derivatives

Ketone

[Acetalde- hyde) Acetone 2-Butanone

2-Butanone

2 Pentanone Allyl methyl ketone

2-Pentanone + 3-Pentanone

2-Hexanone

3-Hexanone

2.4-Di- nitro- phenyl- hydrazonc

of ketone (168)

ketone

- 162-3)

49 50, bz Tetrabromo deriv ,

b p 275 Tetrabromo deriv ,

243, eth , 2,4-Di- nitrophenyl- sulfeny l chloride,

65 6 3,4-Dibromo deriv ,

b p 500-1 5"

Cu salt, 140 red Tetrabromo deriv ,

b p 275 1.2-Dibromo deriv ,

b p 79 5 80 51° 4,4,5,5-Tetrabromo derw , b p 132 6"'

1,2-Dibromo derw ,

b p , 60-21° 3,4- Dibromo deriv ,

66-761Â

K M n 0 4 formic

ac + propionic ac

2,4-Dinitrophenyl- sulfenyl chloride,

65 6

*Derivative data given in order m p , crystal color, solvent from which crystallized

I Heptanonc

tieptdnone Hisptdnone

+

I-Nonanone

2 4 D i nitro phenyl hydrazon,

of ketont

-

Semicar iazone o ketone

140 50'O

2 Dibromo d e r n

b p 9 3 0 5'

I 2 4 5 Tetrd bromo deriv b p

154 5 5 0"'

*Derivative data given i n order m p ,crystal color solvent from which crystallized

174 0 175-6

1 30 -25

Hydration product ( R C r C R ' - RCOCH,R')

and its derivatives

Ketone

!-Nonanone I-Nonanone + I-Nonanone

I-Nonanone +

!-Nonanone

!-Decanone I-Decanone + 1-Decanone i-Decanone 2yclo- nonanone

!-U ndeca-

none 2yclo- decanone

2.4Di- nitro- phenyl- ydrazone

of ketone

55-6

55 6 57-8

55-6

55 6

124

50 1 5 I46

i3

-

emicar- izone of ketone

-

18 20 11-2