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14

The Chemistry of
Alkynes
An alkyne is a hydrocarbon containing a carbon-carbon triple bond; the simplest member of
this family is acetylene, H-C-C-H. The chemistry of the carbon-carbon triple bond is
similar in many respects to that of the carbon--carbon double bond; indeed, alkynes and
alkenes undergo many of the same addition reactions. Alkynes also have some unique chemistry, most of it associated with the bond between hydrogen and the triply bonded carbon, the

:C-H
14.1

bond.

NOMENCTATURE OF ATKYNES
In common nomenclature, simple alkynes are named as derivatives of the parent compound
acetylene:

H3C-C:C-H
methytacetylene

HrC-C:C-CH:
dimethylacetylene

CH3CH2-C:C-CH:
ethylmethylacety-lene

Certain compounds are named as derivatives of the propargyl group, HC:C-CH'-,
the common system. The propargyl group is the triple-bond analog of the allyl group.

644

HC Q-CH,-Cl

H,C-CH-CH,-Cl

propargyl chloride

allyl chloride

in

14.1 NOMENCLATURE OF ALKYNES

645

We might expect the substitutive nomenclature of alkynes to be much like that of alkenes,
and it is. The suffix ane in the name of the corresponding alkane is replaced by the suffix
yne, and the triple bond is given the lowest possible number.

HgC-C-Q-H

cH3cH2cH2cH2-Q-C-CH:

propyne

HrC-CH2-Q-C-H
l-butfne

2-heptyne

HEC-CH-C-Q-CHr
"l

HC-Q-CH z-CHz-C-Q-CH:
1,S-heptadiyne

I

CH:
4-methyl-2-pentyne

Substituent groups that contain a triple bond (called alkynyl grcups) are named by replacing the final e in the name of the corresponding alkyne with the suffix yl. (This is exactly analogous to the nomenclature of substituent groups containing double bonds; see Sec. 4.2A.) The
alkynyl group is numbered from its point of attachment to the main chain:

HC-C-

HC-C-CH2-

ethynyl group
(ethynf + yl)

2-propynyl group

t2

cH2c-cH
3

- (2-

f\
I

propyny')cyclohexanol

\position of triple bond within the substituent

I

position ofthe 2-propynyl group on the ring

As with alkenes, groups that can be cited as principal groups, such as the
group in
-OH
the following example (as well as in the previous one), are given numerical precedence over
the triple bond. (See Appendix I for a summary of nomenclature rules.)

OH

HC:C-CHz-CH-CH3
5 4
2\
'
,{-pentyn-2-ol
\ OH group receives
r

numerical priority

When a molecule contains both double and triple bonds, the bond that has the lower number at first point of difference receives numerical precedence. However, if this rule is ambiguous, a double bond receives numerical precedence over a triple bond.

646

CHAPTER

14

O THE CHEMISTRY OF ALKYNES

j-l

ttl45

HC-C-CH:CHCHT
I

rll

cH3c

tli45

HzC:CHCH2C-CH

-c-cH-cHr

1-penten-4-yne

1-penten-3-yne

-pentyn-3-ene

precedence is given to the double bond
when numbering is ambiguous

precedence is given to the bond that has
lower number at first point of difference

a lrwis structure for each of the following alkynes.
(a) isopropylacetylene (b) cyclononyne (c) 4-methyl-1-p€ntyne
(d) l-ethynylcyclohexanol (e) 2-butoxy-3-heptyne (f) l,3-hexadiyne

14.1 Draw

14.2 hovide the substitutive

name for each of the following compounds. Also provide cofllmon

names for (a) and (b).
(a) cHrcHrcHrcHrc-cH (b)

(c)

OH

"t

cH3cHrcHrcHrc-ccH2cH2cH2cH3

(d)

HC-

I

l

H:C-A-Q-C-CH:

"r.\C:C i

CH:

(e)

/\

H

CH2OCH3

oH
I

HC-C-CH-

14.2

CCHCH2CHzCHT

CH:CH,

STRUCTURE AND BONDING IN ATKYNES
Because each carbon of acetylene is connected to two groups-a hydrogen and another carbon-the H-C:C bond angle in acetylene is 180o (Sec. 1.3B); thus, the acetylene molecule

is linear.

il.ro4

H\cT9-\t

V

i

i;A,

The C:C bond, with a bond length of t.ZO A, is shorter than the C:C and C-C bonds,
which have bond lengths of 1.33 A and 1.54 A, respectively.
Because of the 180" bond angles at the carbon--carbon triple bond, cis-trans isomerism
cannot occur in alkynes. Thus, although 2-butene exists as cis and trans stereoisomers, 2-butyne does not. Another consequence of this linear geometry is that cycloalkynes smaller than
cyclooctyne cannot be isolated under ordinary conditions (see Problem 14.3).
The hybrid orbital model for bonding provides a useful description ofbonding in alkynes.
We learned in Secs. 1.9B and 4.1A that carbon hybridization and geometry are correlated:
tetrahedral carbon is sp3-hybridized, and trigonal planar carbon is sp2-hybridized. The linear
geometry found in alkynes is characterized by a third type of carbon hybridization, called sp
hybridiTation Imagine that the 2s orbital and one 2p orbital (say, the 2p, orbital) on carbon
mix to form two new hybrid orbitals. Because these two new orbitals are each one part s and
one partp, they are called sp hybrid orbitqls. Two of the 2p orbitals (2prand2pr) are not included in the hybridization.

rtion ls ls r- tl Tf- carbon in acetylene atomic carbon: (1s)?(2s)t(2p*)(2py) An sp hybrid orbital. -f$- 2s rrrraffcctcd L-r' hi'Lrn riiz. (c) The two sp hybrid orbitals shown together. on the average. l0l kcal mol-r). Notice that the colors represent wave peaks and wave troughs. is also stronger than the C-H bonds of ethylene (463 kJ mol-r. An .. \ /(spl ^ --f- f I hl"hricl j. 14. Because electron density in an sp hybrid orbital is closer to the nucleus than electron density in other hybrid orbitals.The blue and green . hvlt rid i zirti on 2p )6 )6 '-t'. The reason is that an sp orbital contains a greater fraction ofs character than an sp2 or ansp3 orbital. the C-H bond in acetylene is shorter (1. This bond is an qp-^1p o bond. and 2s electrons are. An sp orbital has much the same shape as an sp2 or sp3 orbital (Fig. One bond between the carbon atoms is a o bond resulting from the overlap oftwo sp hybrid orbitals.2 STRUCTURE AND BONDING IN ALKYNES 647 nn.qp-hybridized carbon atom. The remaining . I I I kcal mol-r. or ethane (423kl mol-r.2. each containing one electron. on the average. 1. compare with Figs. somewhat closer to the carbon nucleus than they are in sp2 or sp3 hybrid orbitals. shown in Fig. qp orbitals are more compact than sp2 or qp3 hybrid orbitals.3 (p.08 A) anA ethane (l.ll A). Table 5. 14. The two remaining whybidized2p orbitals lie along axes that are at right angles both to each other and to the sp orbitals.1 (a) A perspective representation of an sp hybrid orbital. *t )n -f--r : t ^.1.1c.ibitul.14. electrons in an. 648).The "leftover" (unhybridized) 2p orbitals are shown with dashed lines. ip hybrid orbitals are oriented at 180'. closer to the nucleus than 2p electrons.sp orbital on each carbon overlaps with a hydrogen ls orbital to form a carbon-hydrogen obond. is an orbital derived from the mixing of one s orbital and a p orbital of the same principal quantum number. These bonds are sp-1s o bonds.06 Al than the C-H bonds in ethylene (1. p. then.l br./ trough---_\ nodal \_/ surface (a) (b) (c) Figure 14. with a bond dissociation energy of 558 kJ mol-r (133 kcal mol-r).1p hybrid orbital are. The o bonds in acetylene result from the combination of two sp-hybridized carbon atoms and two hydrogen atoms (Fig. has two sp orbitals at a relative orientation of 180".213) shows that the C-H bond in acerylene. (b) A more common representation of an sp hybrid orbital used in drawings.4a). However.rftcctrrr. 2p orbitals peak / wave sp orbital sPo rbiral . In other words. 14.16a and4.

CH:CHz + 106 kJ mol-l ) (25. / zr-electron clensity ilbove ancl belou' the plane of the rnolecLlle EPM of acetylene EPM of ethylene The following heats of formation show that alkvnes are less stable than isomeric dienes: H-Q-C-CH2CHzCH: AHT + l-pentyne 144 kJ mol-t (34. 14. do not participate in o bondcarbon-carbon ing.3.) This bond-strength effect occurs because the C-H bond in acetylene contains a greater percentage of the lower-energy 2s orbital than the bonds derived from sp: or sp3 hybrid orbitals.5 kcal mol-l) H:C-C-Q-CHzCH: 2-pentyne 1. shown as dashed lines. ring of rr-electron densi6. 1a3.S kcal mol-l HzC-CH-CH ?.Two 2p orbitals on each carbon. Notice that the acetylene molecule is literally surrounded by z'electrons.548 CHAPTER 14 . Like the 2p orbitals from which they are formed. Compare this with the EPM of ethylene. they are mutually perpendicular. (5ee Fig. or barrel. which has a'-electron density above and below the plane of the molecule. The total electron density from all of the z'electrons taken together forms a cylinder. Again: hybridization and geometry are correlated.4 kcal mol-t ) .2 sp-sp a bond The o-bond framework of acetylene (shown in blue). and the overlap of carbon sp hybrid orbitals with hydrogen ls orbitals gives the carbon-hydrogen o bonds. about the axis of the molecule (Fig. two rbonds are formed. in contrast. which. 14.4-pentadiene + I29 kl mol-t (30. THE CHEMISTRY OF ALKYNES 2p orbitals sp-ls tr bond 2p orbitals Fltwe 14. Notice that the linear geometry of acetylene results from the 180o orientation of the sp orbitals on each carbon. The leftover 2p orbitals on each carbon overlap to form z'bonds. contain progressively more high-energy 2p character. The two bonding z'molecular orbitals that result from this overlap are shown in Fig. This cylinder of z-electron density is particularly evident in the electron potential map (EPM) of acetylene. Overlap of carbon sp hybrid orbitals gives the o bond. Because each carbon of acetylene has two 2p orbitals.3c).

alkynes because of the dipole moment effect (Sec.4 "C 0.3(a)Attempttobuildamodelofcyclohexyne. at2l20 . @l4. 650).4.7155 g ml-t 0. the sp hybridization state is inherently less stable than the sp' hybridization state. 12. alkvnes have much lower densities than water and are also insoluble in water.3 PHYSICAL PROPERTIES OF ALKYNES A. like a double bond. Acetylene is completely surrou nded by zr electrons. Compare its subility qualitatively to that of cyclohexynrc. However. is more stable in the interior of a carbon chain than at the end.3 PHYSICAL PROPERTIES OF ALKYNES 649 + (b) (a) (c) Figure14.Explainwhythiscompoundisunstable. lR spectroseopy of Alkynes C:C stretching absorption in the 2100-2200 cm-r region of the infrared cm-t in the IR spectrum of loctyne (Fig. 14. explain your answer. B. In other words. Boiling Points and solubilities The boiling points of most alkynes are not very different from those of analogous alkenes and alkanes: HC-C(CHr):CH: HzC-CH(CHz):CH: H:C-CHz(CHz):CH: 1-hexfne 1-hexene 63.3 "C 0.38). Many alkynes have a spectrum. These heats of formation also show that a triple bond. (b) Build a model of cyclodecyne.3 Thetwobondingz'molecularorbitalsinacetylene.(a) Aperspectiveview.6731 g ml-l hexane 68. For example. other things being equal. this absorption is very weak or absent in the IR spectra of many symmetrical. This absorption is clearly evident.14.7 "C point: density: boiling 71. (c) The total r-electron density in acetylene. 14. The blue and green colors in (a) and (b) represent wave peaks and wave troughs.(b) An"end-on"viewas indicated by the eyeball in (a).6603 I ml-t Like alkanes and alkenes. p. or nearly symmetrical. 4-octyne has no C:C stretching absorption at all. for exapple.

5 4 4. the chemical shifts of acetylenic protons are much smaller than those of vinylic protons. The explanation for the unusual proton chemical shifts observed in alkynes is closely re- latedtotheexplanationforthechemicalshiftsofvinylicprotons(Fig.650 CHAPTER 14 .675 cm-r).lic protons 6 4. micrometers 2./Y -H I Although the chemical shifts of allylic and propargylic protons are very similar (as might be expected from the fact that both double and triple bonds involve n'electrons). NMR Spectroscopy of Allqnes Pnoton NMR Spectloscopy Compare the typical chemical shifts observed in the proton NMR spectra of alkynes with the analogous shifts for alkenes: - C-Q-H I -C -f. p.p. An alkyne molecule in solution is tumbling rapidly. 14. C:C sftetching absorption (2120 cm-') lies at considerably higher frequency than C:C stretching frequency (I&C-1. but alkyne chemical shifts are dominated by the effects resulting from one particular orientation of the alkyne molecule relative to the magnetic field.5.14.6 2. an induced electon circu- . :C-H :C-H C. they do not show this absorption. THE CHEMISTRY OF ALKYNES wavelength. 1000 800 600 cm-l Figule 14.8-2.1.7-2. (See Sec.13. /\ H vin1.613).5 H propargylic protons 6 r.The two key absorptions indicated are absent in the spectrum of +octyne.4). This strong.I4. This is a clear manifestation of the bond- The the strength effect on absorption frequency. 12.4 The lR spectrum of l-octyne.8 3 3. When an alkyne molecule is oriented in the applied field Bo as shown in this figure.although the effect is in the opposite direction.2 \/f-f U-U /\ \/ \--\.s-5.8-2. Because alkynes other than l-alkynes lack the unique bond. very prominent in the spectrum of l-octyne (Fig.5 6 7 8 910 13 14 15 16 100 q.34 and Srudy Problem 12. sharp absorption.2 . which occurs at about 3300 cm-I.5 5 5. as shown in Fig. -q | - acefylenic protons 6 1.5 l^-l^ (- alll4ic protons 6 1. is well separated from other C-H stretching absorptions.) A very useful absorption of l-alkynes is the stretching absorption. 5a6.) H80 (\t H60 (s L{ q) (J b20 Or 3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 wavenumber.

3) with that of the other methyl carbon (5 13.\.'. The explanation for these chemical-shift effects is the same one (Fig. of the circulating z' electrons (red) opposes the applied field Bo (b/ue) from the spectrometer in the region of space occupied by acetylenic protons. Because the acetylenic proton lies along this axis. 14.3 13. the local field at an acetylenic proton is reduced.-\ /.7 31. acetylenic protons have NMR absorptions at relatively small chemical shift. f.3 ----_------r- H3C ' 75. lr./ \1 \"/ ll p/ \r ti \'- \. Carbon NMR Spectroscopy Chemical shifts of alkynes in 13C NMR are subject to the in double bonds have same influences as proton chemical shifts.\ / 1 t ll t-. Propargylic carbons.\/= . t aprprlie 11 field I Figure 14.'.t "'.5 Explanation of the chemical shift of acetylenic protons.The induced field B. 583.\ \l I - / / / .14.3c) that encircles the molecule.7 22. Although carbons involved chemical shifts in the 6 100-145 range.2 C 79.4. and propargylic carbons in the lation is set up in the cylinder of zr electrons (Fig.3 PHYSICAL PROPERTIES OF ALKYNES 651 -- \/\. carbons involved in triple bonds absorb at considerably lower chemical shift.' \--l + I 8.8). 13. by Eq.\ ii / t// \. typically by 5-15 ppm. acetylenic protons have NMR absorptions at smaller chemical shift than they would have in the absence of this effect.tt't -/r/ \r--t' . which is much like that of an alkane methyl group./ \ \\ z^t _-\ ll /-''. \. for example. like acetylenic hydrogens.t. \ \ tr \./ \\\\liil l' ".- / .5) discussed for the proton chemical shifts in alkynes. Hence. opposes the applied field along the axis of this cylinder./ \ l. p. The resulting induced field B. As a result. / r . t\ | | I \ r'i'lH\. The chemical shifts in 2heptyne are typical: propargyilc carDons 5 r8. the local field at this proton is reduced.-. Consequently.CH2- 3. .. in the 6 65-85 range. 14.8 CH3 .CH 2.The same effect accounts for the chemical shifts of acetylenic r3C NMR spectra of alkynes. also have smaller chemical shifts.\ \.' circulation fielcl) llqii Irrllllrl s\f I rlzrl \\ .. the chemical shift of the propargylic methyl carbon (6 3.\ l\'.2 C :etvler-ric carbirns CH2 2-heptyne Compare. i I i\c\ i) :i*?fff B1 (indr-rc-ecl ti!' ". Ji\ .

13..4.6.[ llf .4 Identify tbe compound with a molecular mass of 82 that f?|F \ t 0 Figure 14.5 4 4. 14.iti.4 INTRODUGTION TO ADDITION REACTIONS OF THE TRIPLE BOND In Chapters 4 and 5 we learned that the most common reactions of alkenes involve additions to the double bond.ilj-. . For example.3.{ li.I) I Br 2-bromo-l-hexene The regioselectivity of the addition is analogous to that found in the addition of HBr to alkenes (Sec.lJilI.79. r 3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 wavenumber.. he comes to you for an explanation.]. Explain to him why it is reasonable that propyne could have this spectum.) (.) H80 (s . although in most cases they are somewhat slower than the same reactions of comparably substituted alkenes.22.E H60 cd :40 3. As in alkene additions. 6l.X) \ 1000 cm-l 14.6 and the following NlvtR spectmm: 6 1.6 The i 15t6 has the IR spectn. 14. 14. 81. a.652 cHAprER 14 .* shown in (|If.6.1.0 O) Assign each of the resonances in the two spectra to the appropriate carbon atoms. Fig. b20 il. s). SpearumA. THE cHEMrsrRy oF ALKyNES wavelength.7.5 6 T1: n 7 IImi{^ 8 910 11 12 l3t4 Il l.lf. 4. t.4.j{ilf-.'|-L. micrometers 2.' 63. Explain.75.[ Ii.9.5 5 5. 5. Additions to the triple bond also occur. 71. . ..7A): the bromine adds to the carbon of the triple bond that bears the alkyl substituent.i i.6). . the regioselectivity is reversed in the presence of peroxides because free-radical intermediates are involved (Sec.62.83 100 c. @ lR spectrum for Problem 800 600 14.1 Speannt B: 6 12. CH:(CHz)IC:CH l-hexyne * HBr TEHII- CH3(CH2)3C:CHz (I4.2l (9H. Believing this to be an error.6 A student consult€d arwell-known compilation of reference spectra for the proton NMR spectrum of propyne and was surprised o find ttrat ttris $pectrum consists of a single unsplit resonan@ at 61.8. s) (a) March each of the following r3C NIvIR spectra to either 2-hexyne or 3-hexyne.x1. HBr can be added to the triple bond.21.

**d product HrC. 14. : Br: H:C-C t l\l *Br. . In other words.. it is possible to isolate the product of the first addition if one equivalent of HBr is used.2) I -bromo.8D). 4. Br Br HsC-C-C-CH: +HBr € 2-butyne H:C-C:CH-CH: I + HBr I HrC-9-CHzCH: (not isolated) (excess) (14. Ltr. By Hammond's postulate (Sec.3b are destabilized by the polar effect of bromine. not formed In the addition of a hydrogen halide or a halogen to an alkyne. Because the second addition is slower. One of the two possible carbocations (A in the following equation) is stabilized by resonance.stabil ized carbo cation A l I l :Br: l* H:C. 3..C -CHzCHi I .J. stereochemistry not determined (7 4o/o yield) Because addition to an alkyne gives a substituted alkene.14. both carbocations A and B in Eq. I4. 1:B'r.I -hexene.1. I -CHCHT lt H:c-c-cHrcH. The reason is that the halogen that enters the molecule in the first addition exerts a rate-retarding polar effect (Sec.-9-cHzcH: € resonance.CH -CHCHT ( 14.3b) I 'P1. a second addition can occur in many cases.3a) I Br 2.6C) on carbocation formation in the second addition.4 INTRODUCTION TO ADDITION REACTIONS OF THE TRIPLE CHr(CHz):C-CH +HBr ffi BOND 653 CHr(CHz)iCH:CHBr l-hexFne (r4. and this polar effect is only partially counterbalanced by the resonance stabilization in carbocation A. ob*. as in Eq.2-dibromobutane (600/o yield) The regioselectivity of this addition reaction is determined by the relative stabilities of the two possible carbocation intermediates.CH-CHCH: less stable carbocation B I I I I v v rBr t : Br: I H:C. this carbocation is formed more rapidly. the second addition is usually slower than the first.

which gives an aldehyde. The hydration of an alkene gives an alcohol.5c) .5a) OH an alcohol Because addition reactions of alkenes and alkynes are closely analogous. most enols cannot be isolated because most enols are unstable and are rapidly converted into the coresponding aldehydes or ketones. and name of the product. Give the structure. Let's contrast the hydration reactions of alkenes (Sec. cyclohexylacetylene 14. p.8 The addition of HCI to 3-hexyne occurs as an anri-addition. is called hydration. CONVERSION OF ALKYNES INTO ALDEHYDES AND KETONES A. Although the reaction can be catalyzed by a strong acid. see Study Problem 14. However. In fact. f \__J + H2o "o Hs2+.5 . What are the possible stereoisomers that could be formed? 14. stereochemistry. when a combination of dilute acid and mercuric ion (Hg2+) catalysts is used.4) cyclohexyl methyl ketone i9lo/o yreld) The addition of water to a triple bond. HzSo+ R-cH:cH2 + H2o an alkene t R-cH-cH3 (14. and yields are higher. Enl6l). Hydration of Alkynes Water can be added to the triple bond. 4. it is faster.9B) and alkynes. o ( \__J)-C-CH (dilute) lL > ( C-Cu.7 Give the product that results from the addition of one equivalent of Br.7. THE cHEMrsrRy oF ALKyNES 14. like the corresponding addition to a double bond. to 3-hexyne. it might seem that an alcohol should also be obtained from the hvdration of an alkvne: OH + H2o R-c:c-H an alloTne HzSOa' Hs2+ t R-C:CH 2 o4. The hydration of alkynes gives ketones (except in the case of acetylene itself.r"Z""+'\""-. 656).5b) an enol An alcohol containing an OH group on a carbon of a double bond is called an enol (pronounced enols are formed in the hydration of alkynes. oH9 R-C:CH z T> an enol R-C-CU: a ketone (14.'' Hrso.654 cHAprER 14 14.

the reducing agent NaBI{o is the source of hydrogen that replaces the mercury.6b) I I I I R-C-CH Hg* Hg* In the oxymercuration of alkenes.) Dissociation of mercury from this carbocation liberates the catalyst Hg2+ along with the enol. the use of NaBHo is unnecessary in the hydration of alkynes.3b.4A). H l^ | . 5. t/ t( + R-C:CH :ou I ll R-C-CHzl R-C-CHz + .'Ou. ketones. . if an enol isformed as the product of a reaction.) This carbocation reacts with water.Hr0r. The mechanism of alkyne hydration is very similar to that of the oxymercuration of alkenes (Sec. r. p.nce-stabilized carbocation -l Hs* I (Recall that formation of a resonance-stabilized carbocation also explains the position of protonation in HBr addition. This protonation occurs at the carbon bearing the mercury because the resulting carbocation is resonance-stabilized. the oxygen from water ends up on the carbon with the alkyl substituent. 4. 14. which could be in equilibrium with a cvclic mercurinium ion: ----+ R-C-CH _ I \\'Hg* 1' Hgr* R-Q-CH R-C-CH \/Hgt* I (r4. Eq. one part in 108 or less. mercuric ion reacts as an electrophile with the zr electrons of the triple bond to form a carbocation. it is rapidly converted into the corresponding aldehyde or l<etone. (Recall that alkyl substitution stabilizes carbocations. but the equilibrium concentrations of enols are in most cases minuscule-typically.o*fH tOH R-C-CH.5 CONVERSION OF ALKYNES INTO ALDEHYDES AND Most aldehydes and ketones are in equilibrium with the corresponding enols. The relationship among aldehydes. 653.6d) .7C.T. OH OH + R-Q. In the first part of the mechanism.\ *OH /tOH \'l i. and loss of a proton to solvent water gives the addition product.CHz +Ll I Hg* I R-C-CHz + Hgt* an enol (14.T\e important point here is that. The first step in the mechanism of this protonolysis reaction is protonation of the double bond. This protonolysis occurs under the conditions ofhydration.KETONES 655 14. because most enols are unstable. As a result. The reason is that the presence of a double bond makes possible removal of the mercury by a protonolysis reaction.6a) The carbocation is formed at the carbon of the triple bond that bears the alkyl substituent. Hg* Hro* + (14. R-C-CH1 -:oH.<+ I | | I Hg* . However. and enols is explored in Chapter 22. a separate procedure is not required. Sec.

C-CCH'CH. for part (a). @Whichoneofthefollowingcompoundscouldbepreparedbythehydrationofalkynessothatitis uncontaminated by constitutional isomers? Explain your answer. because the carbons of 2-pentyne both have one alkyl substituenl. For part (b).. (In fact. CI{. The hydration of acetylene indeed gives only acetaldehyde. what alkyne starting materials. Remember. Nexg it remains to be shown whether hydration of these alkynes gives ozly the products in the problem.C-C-CHzCHr one alkyl substituent on each carbon HO \-al /\ HrC Hgl \:a' Hg* H:C OH /\ o CH2CH3 H:o+ t tl cH3ccH2cH2cH3 2-pentanone o CH2CH3 Hro+ t tl cH3cH2ccH2cH3 3-pentanone Q4'7) . Protonation of the double bond gives another resonance-stabilized carbocation: n . HC-CH.656 CHAPTER 14 o THE CHEMISTRY OF ALKYNES Conversion of the enol into the ketone is a rapid.) However. acetaldehyde is the only aldehyde that can be prepared by the hydration of an alkyne. Thus. :o tl R-C-CH: ll* . would give the desired products? The equations in the text show that the two carbons of the triple bond in the starting material corre- C:O spond within the product to the carbon of the group and an adjacent carbon. f>H :O' '9H. t( R-C-CHz < -+ a resonance*stabilized carbocation This carbocation is also the conjugate acid of a ketone. This point is explored in Study Problem 14.1. the only possible alkyne starting maierial is acetylene itself. the only possible alkyne starting material is 2-pentyne.6f) The hydration of alkynes is a useful way to prepare ketones provided that the starting material is a l-alkyne or a symmetrical alkyne (an alkyne with identical groups on each end of the triple bond). Thus. a good synthesis gives relatively pure compounds.F:- R-C-CH: + Il-'--LlHl ( 14. if any.Qnrr r--tiu. acid-catalyzed process. hydration of 2-pentyne gives a mixture consisting of comparable amounts of 2-pentanone and 3-pentanone . there is no reason that the reaction of water at either carbon should be strongly favored. H:C. Loss of a proton gives the ketone product. (b) o ll ll CH3CH cH3cH2ccH2cH3 (a) o acetaldehyde 3-pentanone SOlution First.

8b) . 14.(cHj)5f. hydration would give a mixture of constitutional isomerr that would have to be separated. oxidation of the organoborane with alkaline hydrogen peroxide yields the corresponding "alcohol. and the yield of the desired product would be low.acn or .. .5 CONVERSION OF ALKYNES INTO ALDEHYDES AND KETONES 657 I{ence. Consequently. (b) " Dc pr€pe€u Dy a". cH3crHz cH2cH3 H':o'?loH-> | b:a1 \/\ INHOH /3 an enol o tl ----> cHrcH2cH2-c-cH2cH3 (14. hydration would nar be a good wey tb Fepare 3-pentanone. ue'srmqys or 1rj epqtfe{n*ior ur*eu@ i.. 2.CH\ l--'---'\ t\ further to give the corresponding aldehydes or ketones.ffJ" (nl" $'.' 5 {4f cHrcHr-c-cH(cH3L O) Would alkyne hydration te a gooA preparative method for this coryound? Explain.rul \H/3 As in the similar reaction of alkenes. EEEil r+. see Problem 14. (However..pentanone could be preparod by hydration of a different alkyne.c(cH3)3 o ii li.10 Thc hydration of H3 an alkyne is not a reasonabfe prepar*ive rrcnoA for eacb of the folloudng compoxnds.4B). 5. .5A^. ll'.*.) #. As shown in Sec. Hydroboration-oxidation of Al kynes The hydroboration ofalkynes is analogous to the same reaction ofalkenes (Sec." which in this case is an enol.I CH. CH. 14.14.c*ro \. . Explain (c} {a)CF{sCHtCH-g'(b) yhy.> auq/ne oourq e. O " . fi!ffi *. enols react / [cH.9a).o-c$aryzoo O ilt1 tl (cH3)3c-c-cHr cH3ccH2cH2cH3 (c) rr* rorowrng compouxls o ou"trotrVor)A-*o2eH2cH.CH\ / 3CH3CH2C-CCH2CH3 + BH3 -THF* icr"cu" I " --gr"\J \ t\tls t'o.

the reaction conditions can be controlled so that only one addition takes place.-c \ll \ CHt (. if it has a triple bond at the end of a carbon chain). cannot be prevented. these are complementary methods for the preparation of aldehydes and ketones in the same sense that hydroboration-oxidation and oxymercuration-reduction are complementary methods for the preparation of alcohols from alkenes. interfere with a desired reaction. In many cases. van der Waals repulsions. However.e) tz H disiamylborane The disiamylborane molecule is so large and highly branched that only one equivalent can react with a l-alkyne. a second addition of BH.6s8 CHAPTER '14 . / /ll u -(. 5. 5. in this case. however.9. a second addition of BH. as shown. (How would you synthesize disiamylborane? See Sec. Because hydroboration-oxidation and mercury-catalyzed hydration give different products when a l-alkyne is used as the starting material (why?). If the alkyne is a I -alkyne (that is. or steric effects. van der Waals repulsions are used to advantage. to prevent an undesired second addition from occurring: f!-) \l /z rrH cH:(cHz)5-Q-CH THF cH:(cHz)s\ t C:C H/ cH:(cHz)s \/ STUDY GUIDE LINK 14. 70o/o yield) Notice from this example that the regioselectivity of alkyne hydroboration is similar to that observed in alkene hydroboration (Sec. . THE CHEMISTRY OF ALKYNES Because the organoborane product of Eq. 14. + R-C:CH BH3 ---------> multiple addition reactions a l-a$me Howeveq the hydroboration of l-alkynes can be stopped after a single addition provided that an organoborane containing highly branched groups is used instead of BHr.1 Functional Group Preparations \ + L)H (an enol) t-(+) | + Hr( )r oH- lz H t^-f U-U H i cHr(cHz)s-cHz-cH-L) (14. and hydrogen adds to the branched carbon.10) octanal (an aldehyde. is in principle possible.4B): boron adds to the unbranched carbon atom of the triple bond.4B. B-H I represented as (+) \ | BH ( 14.) cH. provided that the alkyne is not a 1-alkyne. One reagent developed for this purpose is disiamylborane. 14. represented with the skeletal structure shown in Eq.8a has a double bond. addition of a second molecule results in severe van der Waals repulsions.

The first addition of hydrogen yields an alkene.. In the presence of Lindlar catalyst. Catalytic Hydrotenation of Allrynes Alkynes. or other amines.9A).6 REDUCTION OF ALKYN ES 65 9 o tl 2) HzOz cH:(cHz)scHz-c-H /OH- cH:(cHz)s-c-c-H o (14. catalyst can be washed with Pb(OAc). 4. quinoline. a second addition ofhydrogen gives an alkane. to give a poisoned catalyst known as Lindlar catalyst. such as pyridine. pyridine ethanol cH3cH zc.12 Compare the results of hydroboration-oxidation and mercuric ion-catalyzed hydratioa for (a) cyclohexylacdylene and @) . 14. 14.14. R-c:c-R catalvst.13) . a Pd/CaCO. hydration of any l-alkyne (otherthan acetylene itself) gives aketone. H2./ C:C.. 2-butyne. like alkenes (Sec.Hz cH2cHzcHi \. + CH3CH2CH2C-CCH2CH2CH3 4-octFne Lindlar catalyst or Pd/C.6 REDUCTION OF ATKYNES A. an alkyne is hydrogenated to the corresponding alkene: H. For example. and certain nitrogen compounds. R-cH:cH-R catalvst > R-cH2-cHr-R (r4.1l) tl cH:(cHz)s-c-cH: Notice that hydroboration--oxidation of a l-alkyne gives an aldehyde. . Hz. undergo catalytic hydrogenation.r2) The utility of catalytic hydrogenation is enhanced considerably by the fact that hydrogena- tion of an alkyne may be stopped at the alkene stage if the reaction mixture contains a catalyst poison: a compound that disrupts the action of a catalyst.. Among the useful catalyst poisons are salts of Pb2+. /\ HH cis-4-octene ( 14.. \r pyriaine quinoline These compowds selectively block the hydrogenation of alkenes without preventing the hydrogenation of alkynes to alkenes.

.:: +' ' . How catalyst poisons exert their inhibitory ef'fect on the hydrogenation of alkenes is not well understood.1s) The reduction of alkynes with sodium in liquid ammonia is complementary to the catalytic hydrogenation of alkynes. 7. If sodium or other alkali metals are dissolved in pure liquid ammonia. In the absence of a catalyst poison. a deep blue solution forms that contains electrons complexed with ammonia (solvated electrons). cH3cHzcHz H L CH3CH zCHz-C-Q-CH zCHzCHr * 2Na + zNn.6A). is a stereoselective syn-addition.6A) RR\ \/f-f U-U /\ HH (14. .9E). are added to the triple bond. 14.$astiw ft) snne as part (a)'with no poison : C:-CH Reduction of Allqnes wlth Sodlum in tiquid Ammonla Reaction of an alkyne with a solution of an alkali metal (usually sodium) in liquid ammonia gives a trans alkene. R-Q-C-R / Na/NHy' / RH r \/l^-f U-U /\ HR trans alkene \ \ Hrlpoisoned \ catalyst (Sec.r*nofthefol@ins. which is used to prepare cis alkenes (Sec.) C*n(CdjsC= I-S$[!P! :. catalytic hydrogenation of allcynes is one ofthe best ways to prepore cis alkenes. like the hydrogenation of alkenes (Sec. In fact. 14.nr. 14. hydrogenation of appropriate alkynes gives cis alkenes. reduction follows from its mechanism.14) octane 4-octyne The catalytic hydrogenation of alkynes can therefore be used to prepare alkenes or alkanes by either including or omitting the catalyst poison.**. +C:C+ \' / /\ H (97o/o 2Na+ -Nn. Thus."r***o* {. the hydrogenation of alkynes.660 CHAPTER 14 o THE CHEMISTRY OF ALKYNES As Eq. in the presence of a poisoned catalyst. l@I.13 shows. CH2CHzCHT yield) (14. . two equivalents of H. .16) cis alkene The stereochemistry of the Na/NH. Pd/c 2Hz noPoison + cH3cH2cH2c-ccH2cH2cH3 t cH3cH2cH2CH2cH2cH2cH2cH3 04. /-\ w*o*i*.

14.68).18a to the right: H' '-J R-C-C-R a" NHr H R-C:C .r1) solvated electron The solvated electron can be thought of as the simplest free radical.i R-C-C-R Na+ (r4.1 8a) a radical anion The radical anion is such a strong base that it readily removes a proton from ammonia to give a vinylic radical-a radical in which the unpaired electron is associated with one carbon of a double bond. The reaction of solvated elecffons with the alkynes begins with the addition of an electron to the triple bond.o / \* + -NHr Na+ ( 14. 6.10B). Remember that free radicals add to triple bonds (Eq. like the unshared electron pair of an amine (Sec. the vinylic radical accepts an electron to form an anion: R C I \_ -r / \ H .1 8c) vinylic radical at equilibrium) Next. The rate constants for the reactions ofthe cis and trans vinylic radicals with the solvated electron are probably the same. --+ Na+ a . 9.2.18d) solvated electron This step of the mechanism is the product-determining step of the reaction (Sec. rapidly undergoes inversion.6 REDUCTION OF ALKYNES Na' + nNH3 (liq) --* + Na+ e-(NH3)o 561 (r4.ZR frl V/ / H AH q R-C:C \JR /w-c/\ RR A\ L-U trans vinylic radical transition state for inversion (strongly favored cis (14. 14. However. and the equilibrium between the cis and trans radicals favors the trans radical for the same reason that trans alkenes are more stable than cis alkenes: repulsions between the R groups are reduced. The destruction of the radical anion in this manner pulls the unfavorable equilibrium in Eq. Such a species is called a radical anion: e. the actual rate of the reaction of each radical is determined by the product of the rate constant and the concentration of the radical. RH \p c-c ffi\ *.653).\ R R Na+ Na+ 14. p.18b) vinylic radical The vinylic radical.Na+ 1n\ R-C:=C-R ( . Because the trans . The resulting species has both an unpaired electron and a negative charge.\/ RH ( t.14.

this is not a serious limitation for the reaction. the trans alkene. The conjugate base of an alkane. the conjugate base of the hydrocarbon is a carbon anion. or carbanion.39.) However. An example of such an ion is the 2-propanide anion: * O V_ sP3 orbital C . Nevertheless.18e) - 42 35 Because ordinary alkenes do not react with the solvated electron (the initial equilibrium analogous to Eq. \ / c:c. The anion formed in Eq. I NHz V pK.14Whatproductisobtainedineachcasewhen3-hexyneistreatedineachofthefollowing ways? (Hint: The products of the two reactions are stereoisomers. because the reduction of l-alkynes to l-alkenes is easily accomplished by catalytic hydrogenation (Sec. over Pd/C (b) with H. 8. THE cHEMtsrRY oF ALKYNES vinylic radical is present in much higher concentration.7 ACIDITY OF I.64).. let's imagine such in which a proton is removed from a hydrocarbon by a very strong base B:-. 14. called generally an allql anion. Recall from Sec. over Pd/C and quinoline and the product of that reaction with D.''b("cHj H -t CH. (This is explored in Problem 14.. - (14. -p-H // + B:- -------> -C:- + B-H a reaction (14. is derived from this radical. the ultimate product of the reaction.18a is too unfavorable).has an electron pair in an sp3 orbital. Acetylenic Anions Most hydrocarbons do not react as Br@nsted acids. Na+ /\ HR + I trans alkene H. @l4.18d is also more basic than the amide anion and readily removes a proton from ammonia to complete the addition. RH \/ Na+ C:C (-\ \R \ RH .. the reaction stops at the trans alkene stage. 14. Z-propanide anion (an alkyl anion) . + -JJH. reduction of alkynes does not work well on l-alkynes unless certain modifications are made in the reaction conditions. 14.) {a} with sodium in liquid ammonia and the product of that reaction with D.662 cHAprER 14 .ALKYNES A.. over Pd/C 14. The Na/NH. pK" /\.19) a carDanlon In this equation.8B that a carbanion is a species with an unshared electron pair and a negative charge on carbon.

generally called an acetylenic anion. and second. Solvated Electrons. The amide ion. the hydrocarbons are simply not acidic enough. However. (14.14.. the sodium salt of an alkyne can be formed from a l-alkyne quantitatively with NaNHr. Na* -:NHz. as an acid. Alkyl anions and vinylic anions are seldom if ever formed by proton removal from the cor- responding hydrocarbons. liquid ammonia. The relative acidity of alkynes plays a role in the method usually used to prepare acetylenic Grignard reagents.2r) Because the amide ion is a much stronger base than an acetylenic anion. STUDY GUIDE LINK 14. hydrocarbons are very weak acids). 8.\ R R-Q C-H ( 14.. is the conjugate base of ammonia. . Recall from Sec. -:NHz.22) In fact.2 Ammonia. An example of this type of carbanion is the l-propenide anion: H:C. has a pK" of about 35. has an electron pair in an sp2 orbital. and Amide Anion B:-+:I. One base commonly used for this purpose is sodium amide. alkynes are sufficiently acidic that their conjugate-base acetylenic anions can be formed with strong bases.or sodamide.8A that Grignard reagents are generally prepared by the reactions of alkyl halides .7 ACIDITY OF 1-ALKYNES 653 The conjugate base of an alkene. dissolved in its conjugate acid. first.35 amide ion (r4. the equilibrium for removal of the acetylenic proton by amide ion is very favorable: n-c:C\u'lNH. An example of this type of anion is the l-propynide anion: sp orbital _t cH3c-c€ l-propynide anion (an acetylenic anion) The approximate acidities of the different types of aliphatic hydrocarbons have been measured or estimated: R:C-H / R'C-C . Because the amide ion is a much weaker base than either a vinylic anion or an alkyl anion. these ions cannot be prepared using sodium amide (Probleml4.l7). which. that carbanions are extremely strong bases (that is.has an electron pair in an sp orbital. alkane alkene alkyne >55 42 25 These data show. 11u* --N!4!L R-C:e: Na+ + iriH. that alkynes are the most acidic ofthe aliphatic hydrocarbons. (:) * \C:C_t-/ sp2 orbital d\ / H H l-propenide anion (a vinylic anion) The anion derived from the ionization ofa l-alkyne.20) H type of hydrocarbon approximate pK. which are reagents with the general structure R-C:C-MgBr. called generally avinylic anion.{Ha:-:NHr+B-H pK.

363).6. Such compounds are not generally available commercially and are difficult to prepare and store. R-C:C-Br. Thus. This reaction is an example of a transmetallation: a reaction in which a metal is transferred from one carbon to another. in this case. the two Grignard reagents in this equation are represented as ionic compounds to stress the acid-base character of the equilibrium.p._. is the acetylenic Grignard reagent.25) Although Grignard reagents are covalent compounds. l3 l kcal mol-1) vinylic (460 C H kl mol-l. which. the elec- tronegativities of the carbons themselves must govern acidity.---r- BrMg+ :CH.CH1 -R -4 ii-('Hr('Hr + BrMg+ -r-:R (11.. CH1CH2CH2CH2-C -C- H + CH-ICH CH3CH2CH2CH2-C-C-MgBr + 2-MgBr ffi an acetylenic Grignard CH3CH3 reagen. then alkynes would be the least acidic hydrocarbons. Bond dissociation energies show that acetylenic C-H bonds are the strongest of all the C-H bonds in the aliphatic hydrocarbons: R I R R:C-H -C-C-H H acetylenic C (548 kJ mol-l. 8.4. What is the reason for the relative acidities of the hydrocarbons? Sec. gthane (a gas) (t4. discussed two important factors that affect the acidity of an acid A-H: the A-H bond strength and the electronegativity of the group A. this one favors formation of the weaker base. 3. 110 kcal mol-l ) (r4. The "alkyl halide" starting material for the preparation of an acetylenic Grignard reagent by this method would be a l-bromoalkyne-that is.664 cHAprER 14 . Fortunately. The release of ethane gas in the reaction with ethylmagnesium bromide makes the reaction irreversible and at one time was also a useful test for l-alkynes."-. Methylmagnesium bromide or ethylmagnesium bromide are often used for this purpose.26) H alkyl C eA2-41S kl mol-l. it is really just another Br0nsted acid-base reaction: {_\ . 96-100 kcal mol-l) If bond strength were the major factor controlling hydrocarbon acidity. Because they are in fact the most acidic hydrocarbons.24) ethynylmagnesium bromide This reaction is extremely rapid and is driven to completion by the formation of ethane gas (when CH. .CHTMgBT is used as the Grignard reagent). However. and the electronegativity differences on aciditv must outweish the effects of bond strensth. THE cHEMlsrRy oFALKyNES with magnesium. Alkynes with an internal triple bond do not react because they lack an acidic acetylenic hydrogen. This reaction is similar in principle to the reaction of a Grignard reagent with water or alcohols (Eq.23) H-C:C-H H-C:C-MgBr + CH3CH2-MgBr -T"F* + CH3CH3 04.27. the relative electronegativities of carbon atoms increase in the order sp3 < sp2 < sp. acetylenic Grignard reagents are accessible by the acid-base reaction between a l-alkyne and another Grignard reagent. Like all Brgnsted acid-base equilibria.

4..14. (Why? See Secs.22and(2)theanalogousreactionofanalkanewith amide ion. than hydroxide or alkoxides. the stabilization of unshared electron pairs is in the order sp3 I sp2 ( sp. Acetylenic Anions as Nucleophiles Although acetylenic anions are the weakest bases of the simple hydrocarbon anions. In aqueous solution. such as S*2 reactions with alkyl halides or alkyl sulfonates (Secs. they are nevertheless strong bases-much stronger.. 91) (b) Use your calculation to explain why sodium amide cannot be used to form alkyl anions from alkanes.15 Each of the following compounds protonates on nitrogen. unshared electron pairs have lower energy when they are in orbitals with greater s character.2).7 ACIDITY OF 1-ALKYNES 555 This trend in electronegativity with hybridization can be explained in the following way.21) l-hexFne (640/o yielcl) n.L . and. in liquid ammonia (Sec. electrons in orbitals with larger amounts of s character are drawn closer to the nucleus. B. 14. 9. Draw the conjugate acid of which compound is m:l:!3el1ft:rtut " ta -:ti-i?rt H:c-cH-NH ^ A rr ^ "'t each. In other words. '/-.7A). Explain.------'Na+ + H. which in turn are closer than spr electrons (Sec.rr. whereas ion A is not. p.----\ | . . Show the resonance structure for ion B.4D. show why stabilization of ion B should reduce its acidity. The alkyl halides and sulfonates. CH3CH2CH2CHrIB. ++ H:C-OHz H:C-CH:OH (b) Ion . nrri.I: I f -bromobutane Na+ :C:CH -"il'r)- sodium acetylide CH3CH2CH2CH2-C:CH * Na+ (14. Is this the acidity order predicted by hybridization arguments? Explain. 14. (Hint: See Study Problem 3.t f B-r: -------> CH3CH2CH2CH2-C:C I CH3CH2CH2CH2- C:C- CH r * Na+ ( 14. They undergo many of the characteristic reactions of strong bases. 10..trl 14.6. 9.17 (a) Using the pK" values of the hydrocarbons and ammonia.16 (a) Ion A is more acidic than ion B in the gas phase.28) The acetylenic anions in these reactions are formed by the reactions of the appropriate 1alkynes with NaNH.*t. In other words. This is a stabilizing effect because the interaction energy between particles of opposite charge (electrons and nuclei) becomes more strongly negative (that is. 14. as in most other S"2 reactions. with the aid of an energy diagram. 14. for example. estimate the equilibrium constantfor(l)thereactioninEq. must be unhindered primary compounds. ^-\r.34). The electrons in sp-hybridized orbitals are closer to the nucleus.) . -t. acetylenic anions can be used as nucleophiles in S*2 reactions to prepare other alkynes. p. on the average. than sp2 electrons. Thus. B lg.5G. Thus. favorable) as the distance between them decreases (the electrostatic law. 113).B is less acidic (c) because it is stabilized by resonance.40.:'zt-. Eq. ion A is less acidic than ion B.9. 14.3.

(a)cHrc:e: Na+ + cH3cH2-I -------> (b)butyltosylate + Ph-C:C: Na+ -------> (cl CH3C:C-MgBr (d) Br(CHz)sBr * ethylene + HC:C: oxide -------> Hro+ t Na+(excess) -------> 14.4-dimetfil-2pentyne using the reaction of H. reaction ofacetylenic anions with alkyl halides or sulfonates (this section) 14.C-C-C: Na+ with tert-bvtyl bromide.2$. 11. 14. Let's review the methods covered so far: l. obtained none of the desired product. then. 14.19) from an alkyl halide and an alkyne.22 Propose another pair of reactants that could be used to prepare 2-heptyne (the product in Eq 14. we stafi with the target molecule and work backward.20 Propose a synthesis of 4.4C) 3.9). notice the stereochemistry of the target molecule: it is a cis alkene.4-dimethyl-2-pentyne (the compound in Problem 14. THE cHEMtsTRy oF ALKyNES The reaction of acetylenic anions with alkyl halides or sulfonates is important because i/ ls another method of carbon-carbon bond formation. the transformation of functional groups. 14.666 cHAprER 14 . 9. @outlineasynthesisofthefollowingcompoundfromacetyleneandanyothercompoundscontaining no more than five carbons: cH3(cH2)6\ /cr{2crl2c}l(cH)2 C:C /\ HH cis-2-methvl-5-tridecene Solution As usual. 11. We've covered only one method of preparing cis alkenes free oftheirtrans isomers: the hydrogenation ofalkynes (Sec. 14. This stipulation is made because such compounds are readily available from commercial sources and are relatively inexpensive.8 ORGANIG SYNTHESIS USING ATKYNES Let's tie together what we've learned about alkyne reactions and organic synthesis.4). The solution to Study Problem 14.21 Outline two different preparations of2-pentyne that involve an alkyne and an alkyl halide. This reaction. in attempting to synthesize 4. and the establishment of stereochemistry (Sec.19 Explain why graduate student Choke Fumely. reaction of Grignard reagents with ethylene oxide and lithium organocuprate reagents with epoxides (Sec. I 8 Give the structures of the products in each of the following reactions. is used in the last step of the synthesis: . cyclopropane formation by the addition of carbenes to alkenes (Sec. 14. Notice that this problem stipulates the use of starting materials containing five or fewer carbons.8) 2.6. First.2 requires all of the fundamental operations of organic synthesis: the formation of carbon--carbon bonds.

14.(94r)eBr(Pqrl+tzgd) t CH3(CHz)'C-CH H2 BTCHzCHzCH(CHr)z cH3(cHz)oc-ccHzcH2cH(cHr)z Lindlar catalvst t NaNHr NHr (liq) - L cH3(cH2)q cH'cH2cH(cH3)2 \/ C:C /\ HH (14. 14."\ C:C /\ HH -CH2CH2CH(CH3)2 2-niethyl-S -tridegrne ALKYNES 667 / (14. 14. To summarize: HC-CH (excess) ffi cHr.29c haq 1161p than five carbons. J\ CH3(CH z)e-C-f. Lina#Ltahst cH2cH2cH(cH3)2 - -. the oderin which they ae intoduced is abitrary. it must be prewere more sodium amide than acetylene. l-nonyne. If there dianion:f. and other reactions would occur.29c) (rarge excess relative to NaNHu) The large excess ofacetylene relative to sodium amide is required to ensure formation ofthe monoanion-thatis.29a) (target molecule) t1t" **1task is to preparc *rc alkyne used - as the sarting naferial in Eq.78): Br-CHzCHzCH(CHE)z -bromo-3-methylbutane --.29e) . some pared as well. This is accomplisbed by forming tlrc conjugate. Ttrerc are two pimary alkyl groups on the tiple bond. Because the l-bromoheptane used in Eq. (What are they?) Because acetylene is cheap and is easily separated ftom the products (it is a gas).8 ORGANIC SYNTHESIS USING cH3(cH2)6. we'll have to use several reaptions that forrn carbon<a6on bonds.29d) l-bromoheptane 1-heptanol The synthesis is now complste.14.29a.:f. I€t's infrodrce the fue+arbon fiagment on tlre right-hand side of this alkyne in tbe las step of the alkyne qmfuis. the anion derived from the removal of only otu acetylene p'roton. H-c-c-H ffi Na+ :e-c-H cHr(cHz)oBr t cH3(cHr6-c-c-H (14. H:o+t l-bronopentane coac HBr CH3CH2CH2CH2CH2GH2CH2-oH Hzsor > CH3CH2CH2CH2CH2GH2CH2-B1 (14. l-bromo3-meflrylbutane (Sec. is prepared by the reaction of l-bromohoptane with the sodium salt ofacetvlene itself.f halide.base aoetylenic anion of l-noryrne and alowing it to rcact with the ap prcpriate commercially available €ve-cabon alk. Because the desired alkyne contains 14 carbons and the problem stiprlates the use of compormds with five q fsw€r carbons. CH3(CHz)o-C:C-H 1 CHI(CHa)5C-C: ffi 1-nonlare CH3(CH2)6-C:-C-CHzCHzCH(CH3)2 04.29b) The staning material for this reaction. The following sequence of reactiols cH3cH2cH2cH2cH2-Br # A Hrc-cH:t will accomplish this objective. use of a large oxcess presents no practical problem.: could fonn.

l2E) -9. It was discovered not long ago that the traditional use of sows in France and Italy to discover buried truffles owes its success to the fact that truffles contain a steroid that happens to be identical to a sex attractant secreted in the saliva ofboars during premating behavior! About three decades ago. 664 illustrate. An example of a pheromone is a compound or group of compounds that the female of an insect species secretes to signal her readiness for mating. scientists became intrigued with the idea that pheromones might be used as a species-specific form of insect control. and for many other purposes. A.24 and 14. . Alternatively. the chemistry of alkynes can be applied to the synthesis of a number of pheromones--rchemical substances used in nature for communication or signaling. and kairomones (plant-derived compounds that function as interspecies signals for host plant selection) are used commercially in this manner. For example. for example.In large-scale agriculture. Attractants for more than 250 different species of insect pests are now available commercially. (a) CHTCH'CH'CH2CH2CH2CH2CH2CH2-OH (b) l-nonanol o tl HrC-C-(CHz)sCH: 2-undecanone 14.568 CHAPTER 14 o THE CHEMISTRY OF ALKYNES 14. might be used to attract and trap the male of an insect species selectively without affecting other insect populations. This strategy has brought about reductions in the use of conventional pesticides by as much as 70Vo in many parts of the United States. The thinking was that a sex attractant.9 PHEROMONES As Problems 14. CH2CH2CH2CH2CH2CH2CH2CH2-O-C-CU' \/\/ C:C C:C /\/\ H:C HH H (9 Z. traps employing mating pheromones are useful as "early-warning" systems for insect infestations. The harmful environmental effects and consequent banning of such pesticides as DDT stimulated interest in such highly specific biological methods. a common pantry moth in the United States) is such a compound: ? H.25 on p. Although experimentation has shown that these strategies are not successful for the broad control ofinsect populations.7). local infestations of the common pantry moth can be eradicated with commercially available traps that utilize the female sex attractant (Fig. Sex pheromones. conventional pesticides need be applied only when the target insects appear in the traps. When used successfully. this strategy would break the reproductive cycle of the insect. aggregation pheromones (pheromones that summon insects for coordinated attack on a plant species).12 -tetradecadienyl acetate (mating pheromone of the female Indian meal moth) Pheromones are also used for defense.23 Outline a synthesis of each of the following compounds from acetylene and any other compounds containing five or fewer carbons. 6Hz. the males of a species might become confused by a blanket of sex attractant and not be able to locate a suitable female. The sex attractant of the female Indian meal moth (Plodia interpunctella. to mark trails. When this approach is used. they are successful in specific cases.

Q -C\/ C:C /\ HrC H CHzCH2CHzCH2CH2CH2CH2CHz. Show how this compound can be converted into the pheromone in a single reaction.The pad on the trap is impregnated with the female mating pheromone.The mating cycle of the moth is thus broken." -l- .7 An infestation of the Indian meal moth.14.Through use of these traps. both the cis and trans isomers of the following alkene were needed. Br - CHZCH2CH2CH2CH2CH2CH2CH z-. 668). a common pantry moth.9 PHEROMONES 669 pad impregnated with mating pheromone Figure 14. fumigation ofthe pantry with insecticides is unnecessary. l4.U ln the course ofthe synthesis ofthe sex athactant ofthe grape berry moth.-. is controlled with a commercially available trap. Males attracted to the pheromone are immobilized and die on the sticky surface of the trap. ) (b) Outline a synthesis of the trans isomer of the same alkene from the same alkyl halide and any other organic compounds. 14. I CH3CH2CH: CHCH2CH2CH2CH2CH2CH2CH zCHz-O { ^ O) (a) Outline a synthesis of the cis isomer of this alkene from the following alkyl halide and any other organic compounds.25 The following compound is an intermediate in one synthesis of the mating pheromone of the female Indian meal moth (structue on p. o HC H2.O tl -C- CH' .

but instead are synthesized from other compounds. Acetylene is so soluble in acetone that most of it actually dissolves.30. is the thermal "cracking" (that is. this substance is not sold simply as a compressed gas.:ig$ Oxygen-acetylene welding is an important use of acetylene. it is explosive. but it is hazardous because. as illustrated by the following examples: :ffi: ' + HCr Hscr:' (1431) ::. CaCr. cao + 3c heat > cac2 + co *'il gfiffi (14.30) -T. The second process for the manufacture of acetylene. and it may become more important in the United States as the use of coal as a carbon source grows.32) Cl chloroprene I::ll"'. at concentrations of 2. decomposition) of ethylene at temperatures above 1400 "C to give acetylene and Hr. PVC) 2HC:CH catalvst > HC:c-cH:cHu vinylacetylene acetylene HCI > Hrc:c-cH:cHz e4. The carbide process is widely used in Japan and eastern Europe.) The most important general use of acetylene is for a chemical feedstock (starting material). although it accounts for a relatively small percentage of acetylene consumption. calciurn carbide Like any other acetylenic anion. cHAprER 14 10 .9:'ffi:1T3.::: (a monomer uded in the manufacture of poly(vinyl chloride). calcium carbide reacts vigorously with water to yield the hydrocarbon. Acetylene itself comes from two corlmon sources.5-80Vo in air.:r?" Calcium carbide is an organometallic compound that can be regarded conceptually as the calcium salt of the acetylene dianion: Q22+ 3(l:Q. Furthermore. The acetylene used for this pulpose is supplied in cylinders. Alkynes do not occur as constituents of petroleum. Acetylene can be produced by heating coke (carbon from coal) with calcium oxide in an electric furnace to yield calcium carbide. because gaseous acetylene at even moderate pressures is unstable. (This process is thermodynamically unfavorable at lower temperatures. 14. As acetylene gas is drawn off. Acetylene cylinders contain a porous material saturated with a solvent such as acetone.67 O 14. and the predominant process used in the United States. more of the material escapes from solution as the gas is needed-another example of Le Chdtelier's principle in action! . THE cHEMtsrRy oF ALKyNES OCCURRENCE AND USE OF ALKYNES Naturally occurring alkynes are relatively rare. the calcium oxide by-product ofthis reaction can be recycled in Eq.

. Pd/C. Lindlar catalyst (c) product of (b) + Or. which spontaneously form the isomeric aldehydes or ketones. a reaction that involves radical-anion intermediates. in the Study Guide and Solutions Manual. Chapter 14. For this reason. The carbons of the triple bond are I I I T Catalytic hydrogenation of alkynes gives cis alkenes when a poisoned catalyst is used. HrSOo. Blarneystyne.26 Give the principal product(s) expected when 1-hexyne or the other compounds indicated are treated with each of the following reagents: HBr (b) Hz. acetylenic Grignard reagents can Alkynes have two general types of reactivity: 1.21 Give the principal products expected when 4-octyne or the other compounds indicated are treated with each of the following reagents: (a) Hz. The carbon-carbon triple bond in an alkyne consists of one o bond and two mutually perpendicular rr bonds. a chemical company of dubious reputation specializing in alkynes.4. Lindlar catalyst (d) product of part (c) + Or. and results in the relatively small chemical shifts observed in NMR spectra. with pq values nea r 25. The reduction of alkynes with alkali metals in liquid ammonia.The induced circulation of these n electrons in a magnetic field shields acetylenic protons as well as acetylenic and propargylic carbons. Inc. in THF. see Section R.28 In its latest catalog. hydrogenation to alkanes occurs. Electrons in sp orbitals are held somewhat cfoser to the nucleus than those in spz or sp3 orbitals. 1 I sp- hybridized. then H'O'/FI2O (d) Na metal in liquid NH.Pd/C (c) Hz. and reduction with sodium in liquid ammonia. alkynes have greater heats of formation than isomeric alkenes.ADDITIONAL I Alkynes are compounds containing carbon-carbon triple bonds. (e) Hg2+. reactions at the acetylenic base sodium amide (NaNHr). 11. in liquid ammonia (h) product of part (g) + CH3CH2I (i) Hgt*. I -C-H bond 1 -Alkynes. then HzO?l-OH 1. then HzOzl-OH 14. The electron density associated with the rr bonds resides in a cylinder surrounding the triple bond.. H2SO4. then (CH3)2S (a) (e) product of part (c) + BH. ln a related transmetallabe formed in the reactions of 1-alkynes with alkylmagne- sium halides. When a poison is not used. (f) product of part (c) * Br.HrO (g) NaNH.are the most acidic of the aliphatic hydrocarbons. hydroboration.Hro (0 BH:. then HzOzl-OH (j) disiamyl borane. PROBLEMS 67 Acetylenic anions are good nucleophiles and react with alkyl halides and sulfonates in Sr2 reactions to form new carbon-carbon bonds. I The sp hybridization state is less stable than the sp2 or sp3 state. addition to the triple bond t Both the hydration and hydroboration-oxidation of alkynes yield enols. 2. Useful additions to the triple bond include Hg'*catalyzed hydration. gives the corresponding trans alkenes. catalytic hydrogenation. Pd/C catalyst (b) Hr. Acetylenic anions are formed by the reactions of 1-alkynes with the strong tion reaction. F'l I ii REACTTON \ {n} REVTEW For a summary of reactions discussed in this chapter.

Inc.. Mr. C-C single bond of propene pounds are th. } 1-butyn-3-ene (d) 5-hexyne {e (a) CHTCHTC:C-D o (b) CHTCH2CDTCD.4S) -CHTCH2CHCHCH2CH2CHtCH: tt DD (f ) octane (g) H.35. from acetylene and any . Al Kyne. C-C single bond of propyne.33 Outline a preparation (cHr).rcH: cH:(cHz)z \/C-C /\ HH of each of the following com- pounds from acetylene and any other reagents. C-H bonds of ethane. THE cHEMtsrRy oF ALKyNES has offered some compounds for sale under the follow- ing names..5-octanediol ( j) (Z)-3-hexen.3-dimethylhexane company's alkynes.34 Using 1-butyne (a ) 2-hexyn-4-ol (b ) 6-methoxy. wrth the stipulation that all of the carbon in the product must come only from the company's alkynes. {a) a stable alkyne of five carbons containing a ring (b) a chiral alkyne of six carbon atoms (c. You have been asked to develop a synthesis of the housefly sex pheromone.1-ol name for each compound. all are incorrect. (a) CHTCH'CD'CD.30 On the basis of the hybrid orbitals involved in the lrl. :it:- ci - cHrqcHr. Explain.H bonds of acetylene (b) C-C single bond of propane.29 In each case. The President. Fragmentary data in a laboratory notebook suggest that the compounds are 1-hexyne.(cHz)_.-16 You have just been hired by Triple Bond. (c) 14. Outline a preparation of racemic muscalure reagents.cH-cH 14.e IR spectra of A and B. propose a synthesis for each of the following compounds.35 A box labeled "CuH. The muscalure will ily observable results. (cl) propyne and 1-decyne 14.l an alkyne of six carbon atorns that gives the same single procluct in its reaction either with BH.67 2 cHAprER 14 . a company that specializes in the manufacture of alkynes containing five or fewer carbons. requisition forms for other fly swatters in case you are successful. lowest first. 14. shown in Fig.ncHr.37 Outline a preparation of racemtc disparlnre.CHTCH. (b) cH:(cHr)3c HC-a:.. Along with the com- in order of increasing length. and C. 14. Propose a correct (f) (CH3)2CHCH2CH2CHTCH-O ( g) cls-2-pentene (h) trans-3-decene (il meso-4. (Don't use spectroscopy. draw a structure containing only carbon and hydrogen that satisfies the indicated criterion.o/Hg2*/H. show how you would distin- subsequently be used in a household guish between the compounds in each of the following pairs. in THF followed by HrOr/-OH or with tl cH3cH2cH2coH (d) 1-butoxybutane (dibutyl ether) (e) the racemate of (3R.n isomers" contains samples of bonds.1.) (a ) cris-2-hexene and 1-hexyne (b) I -hexyne and 2-hexyne be equipped with a laboratory containing all of the (c ) 4.4-dimethyl-2-hexyne and 3. arrange the bonds in each of the following sets three compounds: A. a pheromone of the gypsy moth. m"uscalure.31 Rank the anions within each series in order of increasing basicity. Identify the three compounds. and 3-methyl.1.32 Using simple observations or chemical tests with read- P14. tal CH:CHzQ:-. and one gross of that meets the company's needs. 14. 8. You will O cH3(cH)t-c-oH I 14. (b) 1-hexene muscalure (c) 3-hexanol (d) 1-hexyne (e) fly trap.4-pentadiene.5-hexadiyne as the only source of carbon in the re- actants. needs an outlet for the company's products. (a) C-H bonds of ethylene.o* O tl cHrcH2ccH3 (d ) a six-carbon alkvne that can exist as diastereomers 14. Although each name unambiguously specifies a structure. C. 2-hexyne. cH-.

) (J b20 a 0 3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 wavenumber. 14.: 860 (d Lr :40 q) U b20 o. and explain why an excess of acetylene is important for avoiding this reaction.) H80 (g .38 In the preparation of ethynylmagnesium bromide by BrMg-C-C-MgBr.6 2.8 3 3.8 3 3.5 4 55. (b) Suggest a mechanism for reaction (2).ADDITIONAL other compounds containing not more than five carbon atoms.35.56 7 8 l0 ll 12 13 14 1516 100 a. the transmetallation reaction of Eq. is relatively soluble in this solvent. micrometers 4. cm- 1000 800 1 2. cmFiSure P14.35 lR spectra (l) H-C-Q-MgBr (2) 2H-C-C-MgBr Flgure P14. Two side reactions that can wavelength. (c) Tetrahydrofuran (THF) is used as a solvent because the undesired by-product.: E60 tr (€ L{ :40 q.5 l0 l1 t2 13 t4 1516 l 100 a.s 4 wavelength. 14.-C-H + CH3CHz-MgBr rr* . and explain why an excess of acetylene is important for avoid- -t'(CH2)4CH(CH3)2 H t PROBLEMS 67 3 urrnurlure ing this reaction.38.38 1000 800 I for Problem 14. micrometers 2. P14.s678 4. 0 3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 wavenumber.5 5 5.) H80 (g .6 2.24. ethylmagnesium bromide is ad&d to a large excess of acetylene in THF solution. Explain why it is important for this by-product to be soluble if both side reactions are to be minimized.. A _(CH3(CH)i'J" (- occur in this procedure are shown in Fig. ----> CHTCH3 + BrMg-C-C-MgBr + BrMg-C-C-MgBr H-. (a) Suggest a mechanism for reaction (1).

O: liberates a gas when treated with 14. IR: 3300. (a) CuH. J : ZHz): 63. The absorptions labeled "dry"were obtained on a very dry sample before addition of the acid. (b) When (NHo)rSOo is added to the reaction mixture. + 2RC-Q: 3RC-(T' lH -FffNU * RCH:CHz NMR: 62. s). sorptions at 3300 cm-r and 2100 cm-r and has the following t'C NMR spectrum: 6 2l .41 (1F1. 63.8. doublet of doublets.52 (lH.40 IR: 2100.The integral (as the number of protons) is shown in red over each absorption. Hz 2400 2 100 r 800 1s00 1200 900 600 300 6. strong band at 3350 cm-r Explain this result using the mechanism of this reduction and what vou know about the aciditv of 1alkynes.oO' - 6HzandZHz). (b) Explain how you could distinguish between 1-hexyne and 4-methyl-2-pentyne by '3C NMR.10 (1F1. 1634 cm-I NMR: 53. s) IR: 2110. s).t.43 (6F1. 14.n that shows IR ab- NMR: 63. 52. Explain. J .38 (IH. A trace of aqueous acid was added to the compound before the spectrum was obtained.41 (a) Identify the compound CuH. ppm (6) FiSure P'|4.7 .3.66.31 (3lll. . 5 1. 6Hz) 14. s).40c. chemical shift.10 (2H.J - (3F1.3300 cm-r (c) CoHuO: NMR in Fig. 3300 cm t (sharp) 92.d. superimposed on a broad. s). (d) csH6o the 1-alkyne is converted completely into the alkene. P14.0.The absorptions labeled "wet"were obtained in the presence of aqueous acid.43 (IH.2102. 3300 cm ' lsharp).67 4 cHAprER 14 .40 The NMR spectrum for Problem 14.2Hz). THE cHEMtsrRy oF ALKyNES (b) C4H.40 Identify the following compounds from their IR and J proton NMR spectra. d. 66. J IR: Na+ 2 - ZHz) 125. every three moles of l-alkyne give only one mole of alkene and two moles of the acetvlenic anion: 2RC= RCH-CH.41 (3H. 64.7 Hz disappears on D2O shake A dry 43 chemical shift.79 64. 31.39 (a) When the reduction of alkynes to alkenes by Na in CrHsMgBr liquid ammonia is attempted with a l-alkyne. d.

oo illl HOC-CHzCHz-COH H-COH succinic acid formic acid o (a) Ph-C-CH + Hzo Brz t Ph-A-cH2Br + Ph-Q-C-H THF ph_e_C_D 14. Propose a structure for compound A.8A) Figure P14.5) (f) p'_c-e_ph + HCCI3 (Hint: See Sec. In the absence of a catalyst poison. (A tricarboxylic acid is a compound with HBr (b) NaOD. unlike tertiary alkyl halides. undergo nucleophilic substitution reactions that are not complicated by competing elimination - reactions. 9.c-cH diethylsulfate t t See Sec. to yield succinic acid and two equivalents of formic acid.45 using knowledge or intuition developed from this or previous chapters. which in turn undergoes ozonolysis followed by workup with aqueous HrO. 9.) ri-c-cH ( NaNHz + F-(cHz)s-cl -* I equivalent) (e) neutralize Ph-cH:cHz + Brz 1 NaNHz (H:o+) t (Hint: See Sec. PROBLEMS 67 5 H"i.ADDITIONAL 14.45 Complete the reactions given in Fig. Treatment of A with C2HsMgBr liberates no gas.:i:: the structure orA' and 14.|"?'jl il::il1.) o (c) tl CH3CH2-O-S-O-CHzCHr A cH3(cH (Hint: (d) z)o-. Catalytic hydrogenation of A over Pd/C in the presence of quinoline poison and treatment of the product with O. DzO t t (CH3)3SiCl CH3CH2CHzCHz-C-Q-H + CH3CH2CH2CHz-Li € - (Hint: Tertiary silyl halides. P14. 10. (a hydrocarbon not containing bromine) .42 Propose mechanisms for each of the following known transformations: use the curved-arrow notation where possible.43 A compound A (C6H) undergoes catalytic hydrogenation over Lindlar catalyst to give a compound B.3C. DzO (large excess). and then HrOrgives an optically active tricarboxylic acid CsHr2Oo. hydrogenation of A gives hexane. (a) cH3cH2cH (b) cHrcHzMgBr zcH2c-cH o ll 14.45 K+(cHr)rco- .44 An optically active alkyne A (Cr'Hr+) can be catalytically hydrogenated to butylcyclohexane.