wave lengths at which absorption may occur. REFERENCES
(1) Beattie, W. H., Ph.D. thesis, Uni-
versity of Minnesota, October 1958.
( 2 ) “International Critical Tables,” Vol. V, p. 270, McGraw-Hill, New York,
1926. (3) Landolt, Hans, Bornstein, Richard, “Physika1isch.-chemischeTabellen,” 5th
ed., 3rd suppl., p. 1477, J. Springer, Berlin, 1935. (4) Lowan, A., “Tables of Scattering Functions for Spherical Particles,” National Bureau of Standards A.M.%4, Washington, D. C., 1948. (5) Meehan, E. J., Beattie, W. H., J . Opt. SOC.Am. 49, 735 (1959). (6) Meehan, E. J., Beattie, W. H., J . Phys. Chem. 64, 1006 (1960). (7) Pangonis, W. J., Heller, W., Jacobson, A., “Tables of Light Scattering Func-
tions for Spherical Particles,” Wayne State Universitv Press, Detroit. Michigan, 1957. (8) Penndorf, R. B., J . Opt. SOC.Am. 46, 1001 (1956). (9) Penndorf, R. B., Ibid., 47, 603 (1957). (10) van de Hulst, H. C., “Light Scattering by Small Particles,” Wiley, New York, 1957. RECEIVEDfor review March 28, 1960. Accepted November 17, 1960.
Detection of Olefins by Epoxidation and Hydroxamation and Characterization by Rearrangement of Epoxides to Carbonyl Compounds JACOB G. SHAREFKIN and HARRY E. SHWERZ Department of Chemisfry, Brooklyn College, Brooklyn, N.
Y
b The two most general tests for the
QUALITATIVE DETECTION OF ALKENES
olefin bond, decolorization of bromine and permanganate, give positive signs of reaction with many nonolefinic reducing reagents. Such false positive tests are avoided b y devising tests in which the sign of a positive reaction depends on a chemical change in the substrate rather than the reagent. Commercial 40% peracetic acid transforms olefins to their glycol monoacetates which are treated with hydroxylamine and the hydroxamic acids are detected as the wine red ferric salt. Olefins are also characterized by rearranging the epoxides with boron trifluoride to carbonyl compounds that are then converted to solid dinitrophenylhydrazone. Reactions may b e carried out on a semimicro scale and permit identification of olefins in the presence of acetylenes and other reductants.
Sharefkin and Sulzberg (14) have pointed out that an ideal functional group test should be specific in avoiding both false positive and false negative tests and should be capable of both detecting and characterizing the function in the presence of other functional groups that are either in the same molecule or in different compounds in a mixture. Their test for olefins is based on a Friedel-Crafts acetylation of the carbon to carbon double bond and detection and characterization of the unsaturated ketone with 2,4-dinitrophenylhydrazine. I n accordance with the reactivity selectivity principle, reaction with the more nucleophilic olefinic substrates occurs with all Friedel-Crafts catalysts, but ketone formation with the least nucleophilic substrates requires the most electrophilic catalysts. The classification of olefins into a reactivity spectrum based on the difference in electrophilicity of the catalyst that effect reaction underscores the need for developing a reagent selectivity principle. Detection of organic functional groups that vary widely in their reactivity requires a group of complementary reagents of different reactivity that may be used for the various parts of the reactivity spectrum. i i n ideal reagent for a functional group should also he effective a t the lower limits of the micro or semimicro level for each band of the reactivity spectrum and should also meet the demand of the reagent selectivity principle in permitting the preparation of a suitable derivative in good yield and of sufficient purity for characterization of the substrate. Commercial 40% peroxyacetic acid (4) is specific in transforming olefin substrates to their epoxides under mild
D
the considerable literature, there is no general and reliable reaction for the detection and characterization of olefins (alkenes). The tn-o most general tests for olefin detection, decolori7ation of a 2% aqueous permanganate solution (8, 1 6 ) and a 5% solution of broniine in carbon tetrachloride (9, I S ) , are not specific for the olefin bond and do not occur with many alkenes. Both reagents are oxidants that are reduced by aldehydes, polyhydric phenols, and other reductants as n-ell as by alkynes. The bromine reagent may also be decolorized by substitution with slow evolution of HBr. The nonspecific character of these tests for the olefin functional group is similar to that of tests in which the sign of reaction is based on a chemical change in the reagent rather than in the substrat?. ESPITC
or alkaline conditions and to glycol monoacetates on heating or in acid medium. These monoacetate esters are detected by the Davidson hydroxamic acid test ( 7 ) , which is based on hydroxamation in alkaline methanol solution.
+ CHSCO~H
+
\C-C/
+ HzO
I\\
/I
0
0 .
H
~OCHB
I
1
‘c-c/
/A A‘ I
k
I
+ NH~O-+
‘c-C’ /I
I\
+
0 0
bCHa
I
3 CH3CONHO-
+ Fe+3
I
H H CHBCONHO+
( CH3CONH0)3Fe
The reaction is also used to discriminate alkynes n-hich are epoxidized more slowly, and are cleaved to carboxylic acids under these conditions. Peroxyacetic acid is the acid anhydride of acetic acid and hydrogen peroxide and reacts with hydroxylamine under these conditions to form a hydroxamic acid and give a positive test. The excess of peroxyacetic acid is destroyed before hydroxamation by addition of a trialkylamine which forms an amine oxide. RIN
+ CHaCOpH SPECTRUM
+
RaK40
+ CHsCO9H
OF ALKENE REACTIVITY
Olefins are nucleophiles and the reactivity of their pi electrons depends on the substituents on the unsaturated carbon atoms. Swern (19) has shown VOL. 33, NO. 4, APRIL 1961
635
peroxyacids to function as electrophiles in epoxidation and more recently Lynch and Proskauer (12) applied the Hammett equation to the reaction of peroxybenzoic acid with substituted transstilbenes and obtained a straight line by plotting the sigma values against rate constants. Electron attracting -COOH, -NO?, and -C1 substituents decreased the reaction rate while the electron releasing -OCH3 and -CH3 groups increased the rate and this epoxidation paralleled the reactivity of other electrophiles. CHARACTERIZATION
arrangement product could be predicted from a scale of intrinsic migratory aptitudes developed by Bachman and Ferguson (1).
RI R1--d-C-R~
I II RZ 0
Ingold (11) has related migratory aptitudes to the nucleophilicity of the substituent groups in aromatic substitution, and the steric requirements for the rearrangement have been evaluated by Bartlett ( 3 ) .
OF ALKENES
Olefins undergo addition reactions n i t h a large number of reagents, yet there is no simple method of preparing solid derivatives suitable for characterization because the isomeric products are difficult to isolate and purify. To overcome these difficulties, olefin epoxides mere prepared by carrying out the reaction in ether a t room temperature for 3 to 20 hours, depending on the alkene. Sodium acetate was placed in the reaction miyture to prevent acidcatalyzed cleavage of the epoxide ring. At the end of the reaction, boron trifluoride etherate was added to isomerize the epoxides by a pinacol-pinacolone type rearrangement (IO) to carbonyl compounds which were idmtified by the melting point of their dinitrophrnylhydrazones and also bj- their absorption spectra.
REAGENTS AND SOLUTIONS
40% Peroxyacetic Acid. The coniposition of the regular commercial grade used in these experiments has been described ( 2 4 ) . Tri-n-Butylamine. Eastman grade, S o . 1266, was used without purification. Hydroxylamine, 1M in Methanol. Seventy grams of hydroxylamine hydrochloride (Eastman No. 340), 100 mg. of thymolphthalein (Eastman No. 1091), and 15 mg. of methyl yellon(Eastman No. 338) are dissolved in 1 liter of methanol. A solution of 2 M potassium hydroxide in methanol is then added until the rose color just turns orange. Potassium Hydroxide, 2 X in Methanol. The preparation of this reagent has been described (24). Ferric Chloride, 10% in Methanol. 100 grams of hydrated ferric chloride are dissolved in 1 liter of methanol. Boron Fluoride Ethyl Ether (Purified) Eastman Xo. 4272. 2,4-Dinitrophenylhydrazine Reagent (0.05M in 2 M HC1 in methanol). The meoaration of this reagent has been described (14). Hydrochloric Acid. (2M in Methanol) 169 ml. of concentrated hvdrochloric acid are added to 832 ml. of methanol. v
EXPERIMENTAL PROCEDURE
The structure of the ketones formed may be predicted from the rules for the rearrangement of the analogous 1,2-glycols (20, 21) inasmuch as epoxide rearrangement involves heterolysis of the carbon to oxygen bond and migration of a substituent group by a Khitmore 1,2-shift ( $ 2 ) . Heterolysis is facilitated by electron-releasing substituents and in unsymmetrically substituted eposides the bond which is broken is that between the oxygen atom and the carbon having the least electronegative substituent R1. For symmetrical epoxides, Boeseken (6') found that the group Rz undergoing the 1,2shift possessed the greatest "intrinsic migratory aptitude" and that the re-
636
ANALYTICAL CHEMISTRY
Qualitative Detection of Alkenes. T o 60 mg. of a solid or 0.1 ml. of liquid alkene in a 4-inch test tube, is added 0.3 ml. of commercial 40y0 peroxyacetic acid. If no exothermic reaction occurs, the test tube is heated until the mixture begins to boil. T h e mixture is cooled, tri-n-butylamine is added dropwise until a potassium iodide starch test is negative, and the hydroxylamine hydrochloride reagent is added, then 2 X K O H in methanol until the indicator turns blue, and finally a n additional 0.5 ml. The mixture is heated gently over a low flame, cooled, and 231 HCI in methanol added until the color is pink. One or tn-o drops of ferric chloride reagent are added and the formation of the ferric h l droxaniate is indicated by a wine red or purple coloi. To avoid false positive tests from acid derivatives or alcohols, the compound is subjected t o two control tests. The hydroxamic acid test is first carried out
with the original compound and another sample is heated with a mixture of 86% acetic acid, 1% sulfuric acid, and 13y0water, and the product of this reaction is also subjected to the hydroxamic acid test. These tests determine interferences from either an ester or acid derivative functional group already present in the molecule or from a hydroxyl group that is esterified by the peroxyacetic acid reagent. To rule out other interferences, parallel tests are carried out with peroxyacetic acid, and with the bromine and permanganate reagents, under the conditions given by Davidson and Perlman (8, 9), on both saturated and unsaturated compounds which have representative functional groups in the scheme of qualitative organic analysis. Characterization of Alkenes. One gram of the alkene and 5 ml. of ether are placed in a 25-ml. flask and the temperature kept at 20" C.. n-hile a n equimolar quantity plus a 257, excess of 407, peroxyacetic acid and 5% by weight of sodium acetate are added. T h e mixture is allowed to d a n d from 3 hours for t h e more reactive olefins to 24 hours for the less rcactive ones, poured into saturated &C03 solution to neutralize the acid, the ether layer separated, and the aqueou; layer extracted several times n ith ether. The ether layers are combined, niadc 1113 to total volume of 20 ml.. and dricd for 1 to 2 hours over anh-droll- S U ~ S O ~ . Rearrangement is effertcd -,1 adding 1 ml. of boron trifluoride diethyl ct,her to 10 ml. of the ether solution and >tirring for 5 minutes. After washing \vith 2 ml. of water, separating the ether layer, and distilling off the ether, the residue is treated with 25 ml. of 2,4dinitrophenylhydrazine reagent. the hydrazone filtered off, and the filtrate treated with 2,4-dinitrophenylhydrazine reagent and 2iM HCl in methanol, and heated to precipitate additional hydrazone. The combined 2,4-dinitrophenylhydrazone precipitates are recrystallized from either methanol. methanol and ethyl acetate, pyridine. or other solvents, and thc melting point is determined. Ultraviolet Spectra. The identity of t h e 2,4-dinitrophenylhydrazones was confirmed by comparing the absorption maxima and molar absorptivity of their ultraviolet spectra with literature values or with those of prepared hydrazones from known carbonyl compounds. The Beckman D U spectrophotometer n-as uscd n-ith matched 1-em. silica cells and the concent,rations of 2,4-dinitroplienylhydrazones ranged from 0.00688 to 0.0134 gram per liter of either met'hanol or 95% ethanol as solvent. Where literature values !yere not available, a k n o m dinitrophenylhydrazone was prepared and its ultraviolet absorption values determined. RESULTS AND DISCUSSION
Lower Limits of Detection and Characterization. Cyclohexene was used as a representative olefin for determining the lower limit of detection
of t h e glycol monoacetate produced b y reaction n i t h peroxyacetic acid. K h e n solutions of 0.5 and 1.0 gram of cyclohexene in a solvent were diluted a n d subjected t o t h e qualitative test described above, positive tests were obtained with 1.0 nig. in acetic acid and 5.0 mg. in carbon tetrachloride. Comparison of Alkene Reactivity with Various Reagents. T o determine t h e general applicability of peroxyaretic acid formation of glycol monoaczetates and detection of t h e latter by hydrovamation and treatment n i t h ferric ion, parallel tests were carried out on a large number of olefins n i t h t h e bromine and permanganate reag m t s . With these three reagents, the alkene substrate functions as nucleophile or reductant and t h e order of relative I cactivity of these reagents should parallel their ability to function as osidants. I n Table I, a spectrum of olefin reactivity or nucleophilicity is established b y classifying three conipouncls a i either the most reactive which rcspond to all three reagents, those of intermediate nucleophilicity that g i w tests only n i t h permanganate and bromine reagents, or the least reactive olcfins that r d u c e only the permanganate reagent. The data in Table I show that permanganate is the most reactive and peroxyacetic. acid the lrast reactive of the three rmgents for detecting alkenes. Olefins giving a positive test in the eposidation and hydrovamation reactions usually also react t~ith bromine and permanganate while those which decolorize bromine generally reduce the permanganate reagent also. Exceptions are P-nitrostyrene and allyl carboiiatc, that respond positively in the epo\idation-hydroxamation and permanganate tests but do not decolorize bromine. Detection of Olefins by Epoxidation a n d Hydroxamation. False negative t m t s in t h e epoxidation-hydroxamation tcqts are obtained Tvith olefins having rlectron-attracting halogen, c:iiho\yl, carbonyl, nitro, cyano, and other substituents which decrease t h e nuclropliilicity of t h e alkene. T h e d a t a in Table I indicate t h a t both tei iiiinal and alkyl substituted alkenes rcspond poqitively but that the latter and the cyc*loalkenesreact more readily in accordance with the data of Swern (18, 19). He applied the electronic theories of the English school in relating the characteristics of these compounds to the nucleophilic character and epoxidation of olefins. These observations have been confirmed by Lynch and Proskauer (12) by plotting Hammett sigma values against specific reaction rates for epoxidation and, more recently, in carbene addition to olefins ( 1 7 ) . The parallel between the litera-
Table l.
Spectrum of Olefin Substrate Nucleophilicity with Organic Reagents Sign of Reaction Reagent Permanganate Bromine in CCl, Peracetic acid and hydroxamation Greatest Intermediate Olefin nucleophilicity 2-Pentene hllylamine Alkenes 1-Heptene Triallylamine 1-Dodecene Trichloroethylene 2-Xonadecene Crotonaldehyde 17-Pentatriacontene 2,5-Dimethyl-1,3hexadiene Cyclopentene Cycloalkenes Cyclohexene Indene a- and p-Pinene Limonene Camphene Styrene Arylalkenes 4-17inylpyridine 2,s-Dimethylstyrene
++ +
++
Various Qualitative
+Least Fumaric acid llaleic acid Crotonic acid Srcy lonitrile
Cinnamic acid ol-hnylcinnamic acid
Table II. Relative Specific Rates for Reaction of Olefins and Cycloalkenes with Peroxyacetic Acid in Acetic Acid 0 Oleic acid 36 Cyclobutene 20.4 Rlaleic acid Fumaric acid 0 2-Butene 93 C yclopentene 195 Crotonic acid 0 3-Heptene 110 Cy clohexene 129 Cinnamic acid 0 2-Methyl-2-butene 1240 Methylcyclopentene 2220 Ethylene 0.19 1-Pentene 4 3 1-Octene 5.0
ture values for specific eposidation ratcs in Table I1 and the relative reactivity of various alkenes in the epoxidationhydroxamation tests given in Table I1 suggest that the negative tests with maleic, crotonic, cinnamic, and fumaric acids are attributable t o their inertness to epoxidation rather than to failure of the formation of monoacetate ester on hydroxamation of the ester. While the spectrum of olefin reactivity detected by the eposidationhydrosamation test is somewhat narrower than that of the bromine or permanganate reagents, false negative tests are obtained only with olefins having strong electron attracting substituents on the unsaturated carbon atoms and the test is generally applicable to the different olefins listcd in column one of Table I. Epoxidation-Hydroxamation Test with Other Functional Groups. A n ideal qualitative functional group reagent should not give a false positive test n i t h other functional groups. A comparison of different tests for t h e olefin bond is afforded b y t h e d a t a in Table I11 which contains t h e results of these tests with compounds containing t h e most important functional groups. Although false positive tests are obtained with ketones, iodine, and hydroxyl compounds, the epoxidationhydroxamation reactions are more specific than bromine and perman-
ganate reactions n i t h other functional groups such as aldehyde.. For the olefin, as for the othrr functional groups, there is no single ideal reagent but rather a group of tests n-hich complement each other in avoiding false negative tests by covering the total spectrum of reactivity and which also compensate for the false positive tests of other functional groups. Compounds n i t h labile hydrogen atoms such as fluorene and lrvulinic acid are frequently either subftituted by bromine or oxidized by permanganate so that they give false positive tests. The ure of the epovidation-hydroxxmation reactions t o complement these tests avoids the possibility of erroneous conclusions from such data. The readily osidized aldehyde groups in acetaldehyde, benzaldehyde, and crotonaldehyde decolorize both bromine and permanganate and give false poiitive tests. TI-ith the epoxidationhydrosamation test, negative results are obtained with acetaldehyde and benzaldehyde, but crotonaldehyde gives a positive rraction. Still another advantage of the cposidation-hydroxamation test is its ability to detect a double bond in a molecule that contains the aldehyde group which usually interferes by giving false positive tests. Among the 0thr.r false positive tests from reducing agmts that are ruled out by epoddation hydro-iamation arc> those VOL. 33, NO. 4, APRIL 1961
637
~~
Table 111.
~~
Comparison of Epoxidation-Hydroxamation, Bromine, and Permanganate Tests for Alkenes with Various Functional Groups
Function and Compound Active hydrogen compounds Levulinic acid Malonic acid Fluorene 1,l-Diphenylethane Aldehydes Acetaldehyde Benzaldehyde Crotonaldehyde Alkynes 1-Hexyne 4-Octyne 2-Xonyne 1-Dodecyne Arenes Benzene Biphenyl Triphenylmethane Phenanthrene Anthracene Cycloalkanes Cyclohexane Bicyclohexyl Ethers Amyl ether Isoamyl ether Anisole Phenetole Phenyl ether Bromine and chlorine compounds 0-, m-, and p-Chlorotoluene 0- and m-Bromotoluene Cyclopentyl bromide Iodine compounds Iodoform Isoamyl iodide Methyl iodide Iodohenzene Hydroxyl compounds Methanol 4-sec-Butylcyclohexanol Aldol Phloroglucinol Ketones Acetone Acetophenone Phenylacetone Cycloheptanone (HBr), Compound reacted with bromine with HBr evolution. (b), Positive test was obtained after a few minutes. (E), Disappearance of reagent color was sluggish. (?), Result was ambiguous.
R-LR + CH,COOOH 0 + R-
638
ANALYTICAL CHEMISTRY
+ ROH
C H s~-O-d-H
+
HC1
+
+ ROH
Both aliphatic and aromatic iodine compounds react with the peroxyacetic acid reagent to yield acetate esters that are readily hydroxamated (IS) and the epoxidation-hydroxamation test cannot be used with iodine compounds.
+ CHaCOOOH
RIO
+
0
CHsCOOR A CHsCOWHOH
+ ZCHxCOOH
+ CH3COOOH
C H aO W - H
4- HaNOH
RI
+ CHaCOOH
0
ride to form the ester and then applying the hydroxamic acid test. CHaCOCl
I1
C-0-R
The positive test obtained with anisic aldehyde is accounted for by its oxidation to p-anisyl formate, for this does not occur when anisole is similarly treated.
~~
given by polyhydroxyphenols, aminophenols, and readily oxidized amines. The necessity for using all olefin tests to complement each other is illustrated by the false positive tests given by a number of functional groups in the epoxidation - hydroxamation reactions. Esters, acid anhydrides, and other acid derivatives undergo ready hydroxamation and these false positive tests can be eliminated b y testing the compound with hydrosylamic and ferric ion. Alcohols are converted to acetate esters b y the peroxyacetic acid reagent and false positive tests from this functional group are avoided by using acetyl chlo-
Ketones are attached by peroxyacetic acid in the Baeyer-Villiger reaction (2) to form esters and, therefore, also produce false positive test's under the conditions used for the epoxidation-hydroxamation test for olefins. 0 I1
+ RI(C0CCHa)z + HzO + CHaCOOH
+ CHsCOOH
Characterization of Olefins. Table I V summarizes t h e results obtained for olefins from the controlled epoxidation, rearrangement of epoxide, reaction of the carbonyl compound mith 2,4-dinitrophenylhydrazine1and observed and literature values for t h e melting points and ultraviolet absorption spectra of the dinitrophenylhydrazones. These physical constants are satisfactory for the identification of the alkenes but the over-all yields are low. This is not unpxpected in view of the three consecutive reactions in the procedure, the low yields in peroxyacetic acid epoxidation with less reactive olefins, and the side reactions producing borate esters and dioxolanes in the boron trifluoride catalyzed rearrangements of the epoxide. I n the characterization of a-methylstyrene, the peroxyacetic acid also cleaved the double bond and acetophenone was formed in addition to the expected a-phenylpropionaldehyde. A number of olefins could not be Characterized by this procedure. A mixture of 2- and 3-pentanone is formed with 2-pentene because of the slight difference in migratory aptitude of the methyl and ethyl radicals. I n addition, the presence of geometric isomers of the olefin and its epoxide leads to the formation of mixtures of carbonyl compounds because of the different steric paths for rearrangement. Although anethole and 2,4-dimethylstyrene were detected by the epoxidationhydroxamation test, they could not be characterized and it may be presumed that their reactive olefin bonds are cleaved by the peroxyacetic acid. Difficulty was encountered in crystallizing the dinitrophenylhydrazone product from tetradecene and this alkene could not be characterized. The per cent error in the molar absorptivity indices ranged from 0 to
Table 1V.I
Alkenes and 2,4-Dinitrophenylhydrazones of Carbonyl Compounds Obtained b y Boron Trifluoride Rearrangement of their Epoxides
(Pressure, 760 mm. Hg; t.emperature, 20" C.; specific gravity,
$) 2,4Dinitrophenylhydrazones -
Alkene 2-Methyl-lbutene
95 70
2-Methyl-lpentene
95 70
1-Pentene
95
1-Dodecene
Pract.
Purity
1-Octene
sc
95%
Source B. P. ( " C.) a 30-31" 31 .05c a 62b 61.5-62~ a
(1
d
Allylbenzene
Pract.
(1
2-E t hy l- 1hexene
Pract.
c
1-Hexene
Pract.
a
Styrene
Not specified
0
or-nIethylstyrene
White label
h
1-Heptene
95 %
a
Stilbene
Not specified
a
1-Tetradecene
Pract.
a
2-Pentene
95 7c
30b 30. l C 212-13b 213c 1216
121.6c 15Sb 156-5gC 121b 120.5-121c 63 63.75 146b 145.2C 162b 161-62c 92" 92.8" 123.5 (m.p.)b 124 (m.p.)C 115b 114-5'
Refrac. S ecific Index 8ravity 1.3750b (1) 0.655b 1.3777c (2) 0.6504c 1.3935c (1) 0.69Sb 1,3921" (2) 0.6817s 1,370" (1) 0.645" 1.371OC (2) 0 . 641OC 1.4401b (1) 0.760b 1,4308" (2) 0.7582c 1. 4090b (1) 0.726" 1 .4O9Oc (2) O.715Oc 1.5090" (1) 0 .884" 1.5042" (2) 0.8812c 1.4203b (1) 0.723b 1. 4207c (2) 0.7274c
"
1,3862
(1) 0 . 674b 1 .388OC (2) 0.6773c
yo
Carbonyl Yield Product 19 2-met hyl- 1butanal 7.6 2-Methylpentanal 7 . 8 1-Pentanal 4 . 0 Dodecanal 7 . 3 Octanal
156b 156-7" 2-Ethylhexanal 121b 121c
15
7 . 8 Hexana 1
107" 107" 121b 122c
10.0 Phenylacetaldehyde 136-7" 3 . 8 a-Methylphenylacetal- 136b dehyde 108b (1) 0.705b 5 . 3 Heptanal 107" ( 2 ) 0 .696SC 29 Diphenylacet- 150b aldehyde 150-2c 104-5b ( l ) 0 . i i 2 1 b 6 . 0 Tetradecanal 104c (2) 0.7737s (1) 0.654b (2) 0 . 6 5 0 3
1.5470c (2) 0 .9056c 1.5361b (1) 0.907b 1.5384c (2) 0.9314c
1,43456 1. 4365c
107c
5 . 2 Phenylacetone
1.5440b (1) 0.904b
1,3989" 1 .399lC
M.P. ( " C.) 127" 12gC 102-4" 1034s 107" 107c 106" 106.5c 106-7b
Mn 35Bb 358C 359b 359c 359b 359c 35Sb 357-8' 35Sb 357-8' 36Zb 363" 358" 3531 357b 357-8C 357-gb 357" 357" 357c 358-60b 358' 35Sb 357-81 358-60b 358-91
M x
%
Error 2.1 5 2.2 5 1.97 2 2.0 lo-'
2.2
2.2 2.12 2.16 2.23 2.18 2.2 2.3 2.21 2.26 2.31 2.38 2.2 2.3 2.46 2.31 2.0 2.37 2.43 1.94 2.05
0
2 2 5 2 3 4 7 0
2 5
36b 1.3813b 36.4" 1.3797= The Matheson Co., East Rutherford, N. J. * Experimental values. 0 Literature values d Wallace and Tiernan Products, Belleville, N. J. * The Dow Chemical Co.? Midland, Mich. 1 No literature value available and a dinitrophenylhydrazone was prepared from the carbonyl compound 0 Brooklyn College, Chemistry Dept. Eastman Kodak, Rochester, N. Y. i Philips Petroleum Co., Bartlesville, Okla.
7% and was of the same order of magnitude as many of those reported in the literature. It is attributed to differences in the purity of the reagents and laboratory conditions. ACKNOWLEDGMENT
The authors thank the Buffalo Electrochemical Corp., for the 4001, peroxyacetic acid used in this study, Edward M. Boghosian for assistance with the alkyne tests, and Emanuel Manche for the determination of absorption spectra. LITERATURE CITED
(1) Bachman, W. E., Ferguson, J. W., J . Am. Chem. SOC.56, 2081, (1934). (2) Baeyer, A., Villiger, V., Ber. 33, 1569
(1900).
(3) Bartlett, P. D., Brown, R. F., J . Am. Chem. SOC.62,2927, (1940). (4) Becco Chemical Division, Food Machinery and Chemical Corp., Buffalo 7 , N. Y., Bulletin 4, "Peracetic Acid 40%,1J November 1957. ( 5 ) Bladon, P., J . Chem. SOC.(London) 1953, 2921. (6) Boeseken, J. et al., Rec. trav. chim. 58, 528 (1939). ( 7 ) Davidson, David, J . Chem. Educ. 17, 81 (1940). (8) Davidson, D., Perlman, D., "A Guide to Qualitative Organic Analysis," p. 47, 2nd ed., Brooklyn College Press, Brooklyn, N. Y . , 1958. (9) Ibid., p. 48. (10) Heussler, K., Wettstein, A., Helv. Chim. Acta 36, 398 (1953). (11) Ingold, C. K., "Structure and Mechanism in Organic Chemistry," p. 474, Cornel1 University Press, Ithaca, N. Y., 1953. (12) Lynch, B. M., Proskauer, K. H., J . Chem. SOC.(London) 1955, 1525-31. (13) Sharefkin, J. G., Shwerz, H. E., ANAL.CHEM. 32, 996 (1960).
(14) Sharefkin, J. G., Sulzberg, T., Ibid., 32, 993 (1960). (15) Shriner, R. L., Fuson, R. C., Curtin, D. Y., "Systematic,, Identification of Organic Compounds, p. 106, 4th ed., Wiley, New York 1956. (16) Ibid., p. 133. (17) Skell. P. S..Garner. A. Y.. J . Am. Chem. soc. 78.' 3409 (1956) (18) Swern, D., Chem. Rev. 45,5 (1949). (19) Swern, D., J . Am. Chem. SOC.69, 1692 (1947) -. ,. IT;., Zincke, T., Ber. 29, (20) 7rhoerner, ,----~ 2158 [ 18Yfj). (21) Tiffeneau, M., Tchoubar, B., Compt. rend. 207, 918 (1938). (22) Whitmore, F. C., e t a l . , J . Am. Chem. Soc. 54, 3274, 3431 (1932); 55, 4161 (1933); 61, 1586 (1939). \ - -
RECEIVEDfor review August 31, 1960. Accepted November 29, 1960. Meetingin-Miniature, Metropolitan-Long Island Section, ACS, New York, March 1958. Based on the M. A. thesis of Harry E. Shwerz, Brooklyn College, June 1960. VOL. 33, NO. 4, APRIL 1961
639
