AD-Ri51 567 THERHOLYSIS OF 4-METHYL-4-(I-PROPENYL)HALONdVL PEROXIDE: i/iMECHANISTIC LIMIT-.(I) ILLINOIS UNIV AT URBAINA DEPT OFCHEMISTRY J E PORTER ET AL- 28 FEB 85 TR-37 N

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SIMUNITY CLASSIVICATION OF TWO$ PA@UIW(in' D4010 BSm'm'

OFFICE OF NAVAL RESEARCH

Contract NO0l 4-76-C-745

Task No. NR-051 -61 6

TECHNICAL REPORT NO. NJ014-76-C-O7 1 I5-37

Therrnolysis of 4-Methyl--4-(-propenyi)malonyl Peroxide:

Mechanistic Limits to Chemiluminescence Efficiency

by

Judith E. Porter and Gary B. Schuster

Prepared for Publication

in

Journal of Organic Chemistry

School of Chemical. Sciences

Univers7ity of Illinois

Urbana, Illinois 61801

Fetu-uary 2,199b

Reproduction in whete orin part is permitted for

any purposes of theiln- rtd St,.ies Government

Approved for Public Deev':[istribution Unlimited.

0Vp -o

Theriolysis of 4-Methyl--(l-propenyl).alonyl Peroxide:

Mechanistic Limits to Chemiluminescence Efficiency

Judith E. Porter and Gary B. Schuster*

i

Department of Chemistry

oger Adams laboratory

University of Illinois

1;rhana, Illirnois 61801

I

-I-

'*1

Ki

r".

H!

•T. 17 T V. V_ . .. . .r

Abstract: The preparation and thermal chemistry of 4-methyl-4-(1-propenyl)-

malonyl peroxide (3) is described. Thermolysis in acetonitrile at 840C gives

2,4-dimethylbut-2-ene-4-olide in 45% yield and an oligomeric ester derived from

an intermediate c-lactone in 55% yield. The reaction of 3 can be catalyzed by

aromatic hydrocarbons such as perylene. Under these conditions weak chemilumi-

nescence results. The mechanism for light generation is identified as chemi-

cally initiated electron-exchange luminescence (CIEEL). Application of the

CIEEL mechanism to 3 reveals an important limitation to light generation by

this path.

.4

K,

4J

4.

4'

4 :: ' '"' - "- " " " " '-' .: .,-- .i.. " " :. ." -" : , " - .- -,.; ' : L " . - ,''- . -. -"- '' - ; -'- ., , . .- '' .

Chemical reactions that generate visible light often arouse interest. This

phenomenon is observed to occur naturally in bioluminescent organisms I and it

can be created synthetically in the laboratory.2 The organic substances that

are known to exhibit chemiluminescence with measurable efficiency are limited

to structures containing a peroxide linkage. This constraint is related

directly to the energy required to generate light. The exothermic conversion

of the oxygen-oxygen bond of the peroxide to some other functional group is one

of the few transformations capable of releasing sufficient energy to generate a

visible photon.

Satisfaction of the energy requirement outlined above is a necessary but

not a sufficient criterion for the design of an efficient chemiluminescent

reaction. Successful routing of the released energy to the creation of an

electronically excited state product must also occur. The details of this

routing are revealed by studying the mechanism of chemiluminescent reactions.

Our previous efforts in this regard have revealed a general pathway we identi-

fied as chemically initiated electron-exchange luminescence (CIEEL).3

Malonyl peroxides are endowed with many of the features required for the

efficient generation of chemical light by the CIEEL path.4 In their simplest

form, these substances lack an efficient path for energy release. Recently, we

reported investigations of the chemiluminescence of cyclopropyl-substituted

malonyl peroxide 14 and 4-methyl-4-phenylmalonyl peroxide (2)5 . Both of these

high-energy compounds do generate light by the CIEEL route. Herein we report

our investigation of the thermal and chemiluminescent, properties of 4-methyl-

K-

2

4-(1-propenyl)malonyl peroxide (3). This compound also is weakly chemilumi-

nescent, and its investigation reveals clear mechanistic limits to light

generation by the CIEEL route.

==H HC' /Ph H 3C-=, CH3

0 0 0-0 0-0H3C

0--0

2 3

Results

Synthesis of Peroxide 3.

No malonyl peroxides have been reported that include olefinic functional

groups as part of their structure.6 The predictable sensitivity of the double

bond to the usual acid-catalyzed oxidative cyclization conditions probably

served to inhibit attempts to prepare these compounds. Indeed, we were unable

to develop a synthesis of 4-methyl--(2-styryl)malonyl peroxide. However, the

synthesis of 3 proceeds smoothly, but in relatively low yield, under these

conditions from the malonic acid. The preparation of 3 from a mixture of

cis-and trans-2-methyl-2-pentenoic acid 7 is outlined in eq. 1. Details of

these reactions are given in the Experimental section.

C*3 CH3 I) LDA H3C--- H202

CO2 H 2) CO 2 H0 2 C- NC02 H CH3 SO3 H/Et 2 o

*. o'***.- "o *% -" .'*** •°%° - . . *..• -. . . . * . • . f . ... ....

3

Peroxide 3 is isolated by column chromatography on silica gel at -200C as

a mixture of cis- and trans- isomers. The 1H NMR spectrum shows that the two

isomers of 3 are present in a ca. 1:1 ratio. All attempts to separate these

Isomers were unsuccessful. The mixture was used in the subsequent investigati-

on of the thermal and chemiluminescent properties of this peroxide.

Thermolysis of Malonyl Peroxide 3.

The thermal reactions of 3 were investigated under a range of conditions.

Heating a nitrogen purged acetonitrile solution (8x10-3M) at 840C for 1 h gives

a white solid identified as oligomeric (n-5) ester, 4 in 55% yield and 2,4-

dimethylbut-2-ene-4-olide (5) in 45% yield, eq. 2. Based on the behavior of

6oother malonyl peroxides, we presume that. the oligomeric ester is derived from

a-lactone 6, which is the primary product. formed by decarboxylation of 3, eq.

3. The butenolide (5) was identified by comparison with an authentic

H3C- 0 3 CH CN C- oj11 - , CH 3 (-0--0C I CIT-1n0 1

3I0

0-0-33 4

H C-= CH3 -

-0

2

p

S

sample prepared by the procedure of Gorewit and Rosenblum. Oligomeric ester 4

was characterized spectroscopically and by its molecular weight (osmometric).

There Is no detectable chemiluminescence from the reaction of 3 under these

conditions.

The CIEEL mechanism relies on an initial electron transfer from an

activator (ACT, typically an aromatic hydrocarbon) to the peroxide for initia-

tion. Thermolysis of 3 in acetonitrIle containing perylene (3x10- 3 M) gives

products 1 and 5 in unchanged yields and low intensity, but easily detected,

chemiluminescence. The chemiluminescence emission spectrum is identical with

perylene fluorescence. Similar results are obtained in benzene solution (the

yields of light and 5 are lower) and in the presence of 02'

The rate of reaction of peroxide 3 was studied, in part, to confirm that

it is the source of the observed chemiluminescence. The thermal reaction was

monitored both by infrared spectroscopy and by chemriluminescence. The rate of

consumption of 3 (IR, 1804 cm-7 ) is the same as the rate of chemiluminescence

decay, Table 1. Moreover, it was observed, as expected from the CIEEL mecha-

nIsm, 3 that perylene (and other ACT) accelerate the reaction of 3 according to

the kinetic law displayed in eq. 4. These data also are

kobsd k1 + kACT [ACT] (4)

summarized in Table 1. The chemiluminescence intensity is directly propor-

tional to the concentration of malonyl peroxide 3 and depends inversely on the

one-electron oxidation potential of ACT. The data are displayed in Table 2.

There is much less light formed from 9,10-dibromoanthracene than from 9,10-

diphenylanthracene. This result helps exclude mechanisms requiring energy

transfer from an initially formed excited state of 5 or 6 to the ACT.9

The temperature dependence of the ACT catalyzed chemiluminescence of 3 is

particularly helpful in analyzing this reaction. Chemiluminescent reactions

provide the unique opportunity to measure both the temperature dependence of

the consumption of the peroxide and the instantaneous rate of formation of the

excited product.1 0 The first is determined from conventional analysis of the

temperature dependence of the reaction of 3 and corresponds to the activation

energy for the rate-determining-- step in the mechanism. For the ACT catalyzed

process, the rate limiting step is characterized by kCAT and its temperature

dependence gives E aCAT The temperaturp dependen ,,e of the chemiluminescence

intensity (EaCHL) contains contributions not only from the rate-limiting-step

(EaCAT), but also from - term(s) that r-flects the partitioning of an interme-

diate between a path ultimatl.Iv leadirg, tc light (Elig ht) and one not giving a

photon as a product (Ea . This is exressed mathematically in eq. 5. Thus,

ifEaCHL is greater than CATaa

CHL EaCAT Iiwh-. lark. (5)

there Is an intermediate in thf, r,-i -, s,:-uence leading to light, and this

intermediate must proceed over, a w ; bjrrier to stay on the "light-path"

than to get off of it.

The activation energies F ' AT, ir '1 w,-r& determined by measuring the

temperature dependence of kAT -mil t!,- lonui.imnescence intensity. The data

are summarized in Table . The vail cf a r AT for perylene in acetonitrile is

6

10±1 kcal/mol and that of EaCHL is 14+1 kcal/mol. Thus, analysis within the

model described above shows that there is an intermediate in this reaction that

can proceed to give light by a path that has a barrier ca. 4 kcal/mol higher

than one leading only to ground state products. This helps to explain the low

yield of light obtained from malonyl peroxide 3.

Discussion

The chemistry of simply substituted malonyl peroxides is well understood.

Thermolysis leads to oxygen-oxygen bond cleavage, decarboxylation, and 1,3-

closure to give an a-lactone, eq. 6.6 The heat of reaction for this

R1 -R2 RR 1 R 2 R

S 0 RI N<!R2 R, R/R2

A 02 C 2 -- co 2 0 6)

0-0 0 ,1O

* sequence, estimated using Benson group equivalents, 1 is ca. 30 kcal/mol. This

is not a sufficiently exothermic process to generate a photon of visible light

in high yield. Catalyzing this rea(7tion by electron transfer within the CIEEL

mechanism simply lowers the activation energy and makes light generation even

less probable. Inspection of eq. 6 readily reveals that much of the energy of

potential use for excited state formation from the malonyl peroxide is used up

instead as strain in the three membered ring lactone. Our investigation of

malonyl peroxide 3 was undertaken with the hope that its reaction to form

butenolide 5, whicA is exothermic by na. Q0 kcal,mol1 1 , would forestall the

"energy-wasting" formation of 6-.atono 6. indeed, this does occur. The yield

of 5 is ca. 50% in acetonitrile in both the un-catalyzed and the perylene

catalyzed reaction. However, the yield of light in these reactions is still

• . , . . " • • , ,.S, . .

* 7

dissappointingly low. We did niot measure the ehemiiumineseence quantum yield,

* but, by comparison with other, r'eactionis, we ean eoncelude with certainty that it

Is considerably less than 1%. Since the energy requirement for efficient

* chemiluminescence is satisfied, the .low yield from 3 must represent a mechanis-

* tic limitation.

Scheme I is the mechanism we propose for tho ACT-catalyzed reaction of

malonyl peroxide 3. It is consistent with all of the results reported above,

with the behavior of other malonyl peroxides, and with other cherniluminesceit

reactions known to proceed by the CIEFL path.

The first step in the proposed mechanism is the thermally activated

transfer of an electron from ACT to the peroxide -~q. 7. This probably occurs

* during the cleavage of the oxygen-oxygen bond and is followed rapidly by (in

concert with ?) loss of Cn. to give r-adiir-a anion 7. There are two

Scheme I

-H 3 C- .=\CH3 k H3C-==\ ,CH 3 +

0 1 ' ACT ---- .0OC' ACT* (7)

H3C -C+ -CO 2 H3C-- CH 3 +

ACT* 0- ACT* (8)C"C0 2 - 0-,

7H3C C 3 H3C, - C 3 C

ACT-*~ ACT'--b+ + ACT (9)

*7 8

_ ACT -- - 5 ACT light + ACT (10)

H3 C 3 internal- - 3~ --)-CH - __ -,

9 8

configurations for 7. The one shown in Scheme 1 has a cis-allyl structure and

can close to give the butenolide. The alternative structure has a trans-allyl

geometry and cannot close to 5. These isomers probably do not interconvert

during the lifetime of 7 (or 8, or 9) and the ratio of 5 to 6 ultimately

* observed is set by the conformation of the intermediate during decarboxylation.

I Radical anion 7 is in its electronic ground state. As outlined in eq. 9,

* it can partition between two paths. One of these, closure to the radical anion

of butenolide 5 leads eventually to light, eq. 10. The other, back electron

transfer to ACT., leads to zwitterion 8 and is a step off the light path.

Consideration of the values of E aCAT and EaCHL leads to the conclusion that the

back electron transfer has a barrier which is ca. 4 kcal/mol less than the

closure to the butenolide radical anion. This competition limits the yield of

light, and points to an important criterion that must be satisfied in order to

generate light efficiently by the CIEEL route. We will return to this point

below, but first it is interesting to consider biradical 9 in a little more

detail. The uncatalyzed thermolysis of peroxide 3 can reasonably be thought of

as generating biradlcal 9. It is likely that 9 is an electronically excited

state. The ground state of this structure is reasonably represented as the

zwitterion 8. It is not possible to estimate easily the energy difference

between 8 and 9, but we feel confident that 8 is lower. With this conclusion

in mind, the formation of 9 is a chemiexcitation. That is, a ground-state

species reacts to form an electronfolly excited state product. However, this

excited state is useless if light generation is the goal. It does not emit,

and its lifetime is probably too short (Q 8, fast) to permit energy transfer to

9

an emitter even in the unlikely event that its excitation energy (AE9 -8 ) is

great enough to create a visible photon. Thus, malonyl peroxide 3 does form an

excited state (9), but the characteristics of the state prohibit luminescence.

Finally, it is instructive to compare the reaction of dimethyldioxetanone

12(10), a peroxide known to generate light efficiently by the CIEEL route, with

malonyl peroxide 3. A partial mechanism for the chemiluminescence of 10 is

shown in Scheme II. The first step in the sequence, eq. 12, is exactly

Scheme 11

0_:*0-0 k 0

+ ACT ACT ACT* (12)0 3H 3 CH 3

CH 3

10 11

0 IIACT- ACT ACT (13)

HC CH3 -CO 2 , CH 3 -- CH 3

3 0 CH 3 0 CH3

analogous to eq. 7 in the reaction of 3. However, back electron transfer from

radical anion 11, eq. 13 is probably endothermic (oxidation of an alkoxy

radical' and cannot compete with the decarboxylation of 11. Comparison of this

step with the competition outlined in eq. 9 pinpoints the mechanistic limita-

tion to light generation from 3, and, by extrapolation, from all malonyl

peroxides. The required rapid decarboxylation, eq. 8, generates a carbon

centered radical that can be oxidized by ACTk and thus removed from the light

* - *-*

10

path. This feature Is endemic to malonyl peroxides. So, with this knowledge,

we can conclude with some certainty that, despite a great deal of promise, 4

malonyl peroxides are not useful as chemiluminescent reagents.

Experimental

General. Proton magnetic resonance spectra were recorded on a Varian

Associates EM-390 or XL-200 using tetramethylsilane as the internal standard.

IR spectra were recorded on a Nicolet 7199 FT-IR or a Perkin-Elmer 1320

instrument. Gas chromatographic analyses were done on a Hewlett Packard 5790A

or a Varian 3700 gas chromatograph both equipped with a flame ionization

detector. UV-Vis absorption spectra were recorded on a Perkin-Elmer 552

spectrometer. Fluorescence spectra were recorded on a Farrand Mark I Spectro-

fluorometer or by photon counting to permit direct comparison with chemilumi-

nescence emission spectra. Elemental analyses, active oxygen, and molecular

weight determinations were performed by the Analysis Laboratory, Department of

Chemistry, University of Illinois, Urbana, lLlinois.

Chemiluminescence Measurements. Chemiluminescence measurements were

performed as described previously.1 3 Sample temperature was regulated to

within 0.10 C by means of an electrically heated cell holder. In a typical

experiment, a solution of peroxide and ACT was placed in a Pyrex cuvette

equipped with a Teflon stopcock. The cuvette was placed in an electrically

heated cell holder. After thermal equilibration (4-6 minutes) the chemilumi-

nescence decay was monitored at the fluorescence maximum of the activator. The

rate constant was determined by least squares analysis. The kinetics were

found to be strictly first-order, and independent of peroxide concentration in

all cases.

7...... . ...- .........' ' , :,, -- " "- '. -. -,"'- " • .-' "*'-*'. •*.. .f. - .- . -. . * ..-'-" .* . -

Ethyl 2-Methyl-2-pentenoate. A solution of the anion of ethyl a-diethyl-

phosphonopropionate was prepared by adding the phosphorus compound 14 (46g,

0.19mol) slowly to a slurry of excess NaH (13g of 50% oil dispersion, 0.27mol)

- .in dimethoxyethane (400mL) while maintaining the temperature below 200 C with an

ice bath. After stirring for I h at room temperature, propionaldehyde (14.5g,

0.25moi) was slowly dripped into the reaction mixture while maintaining the

temperature below 350 C with the ice bath. The mixture was stirred at room

temperature for 20 min, then diluted with 200mL H2 0. The aqueous mixture was

extracted 4 times with 75mL of ether, the organic layers combined, dried over

MgSO4 , and the solvent removed in vacuo. Distillation of the residue yielded

12.84g of the ester (0.09mol, 417.5%): bp 60-650C (18mm) (lit. 1 5 = 60-630C

* (18mm)); NMR (CDCl 3 ), 66.75 (t, IH), 14.20 (q, 3H), 2.20 (m, 2H), 1.88 (s, 3H),

1.34 (t, 3H), 1.13 (t, 3H).

2-Methyl-2-pentenolc Acid. The ethyl pentenoate (6.84g, 0.048mol) was

added to a solution of KOH (5.6g, 0.10mol) In 15OmL MeOH and 150mL H2 0. The

mixture was heated at reflux for 0.5 h, cooled, poured over 1Og ice, and

washed twice with 100ml. portions of ether. The ether washes were extracted

with 5OmL 10% aqueous Nall and the basic, aqueous wash added to the aqueous

reaction solution. The reaction solution mixture was then acidified to pH 3

with 6M aqueous HCI, then extracted four times with 5OmL portions of ether.

The organic layers were nnmbined, Aried over MgS0 4 , the solvent removed in

vacuo, and the residue distilled to yielcJ 4.2g of the acid (0.037moi, 77%): bp

70-730C (1mm) (lit.1 6 bp 106.50C (10mm)); NMR (CDCl 3), 66.86 (t, IH), 2.21 (m,

2H), 1.814 (s, 3H), 1.06 (t, 310.

.-, . . . . . . . . . .

4 12

I-Methyl-i-(1-Propenyl)Malonic Acid. A solution of LDA was prepared by

adding 235mL of 1.5M n-BuLl In hexane (2 eq) to a dry THF solution (500mL, Na,

benzophenone) of dilsopropyl amine (17.68g, 0.350mol, 2 eq) at OC. 2-Methyl-

2-pentenoic acid (20.Og, .175mo1) was dissolved in 50mL dry THF and the

solution added slowly to the LDA solution at OOC. The solution was stirred for

1.5 h at OC and then cooled to -780C with an IPA/CO2 bath. Dry CO2 was

bubbled through the solution for 45 min at -780C and 30 min at OOC. The

reaction solution was diluted with 200mL H20, acidified to pH 3 with 6M HCI,

and extracted three times with 150mL ether. The organic layers were combined

and extracted three times with 10OmL of 10% aqueous NaOH. The combined basic

layers were acidified to pH 3 with 6M HCl and extracted with 3 100ml portions

of ether. These final ether layers were combined, dried over MgS04 , the

solvent removed in vacuo, and the residue recrystallized from 1:4 ethyl

ether/pentane to yield 11.85g of the malonic acid (0.075mo, 43%): mp 137-

1390c; NMR (CD3 CN), 65.71 (m, 211, 1.70 (d, 3H), 1.52 (s, 3H).

Anal. Calcd for C7H1I 0O4 : C, 53.16; H, 6.33. Found: C, 53.61; H, 6.78.

4-Methyl-4-(1-propenyl)malonyl Peroxide. (3) The malonic acid (1.0g,

0.0063moi) was added to a solution of 3 mL CH 3SO 3H in 15 mL of ether at O°C

under N2 . Hydrogen peroxide (90%, 3mL, o.ollmol) was added dropwise to the

cold solution at a rate that kept the temperature below 100C. The reaction

solution was stirred at room temperature for 4 h, poured over 50g of crushed

ice, diluted with 50mL of aqueous saturated (NH4)2SCO4, and extracted four times

with 25 mL portions of ether. The organic layers were combined, dried over

MgSO 4 , and the solvent removed in vacuo. The residue was chromatographed on

silica gel with 10% ether/pentane at -200C. This gave 75.8mg of malonyl

peroxide 3 as a mixture of the cis and trans isomers (0.49mmol, 7.8%): NMR

* .,. -...... ...........*.. ... . . •- - . , .* *. * . 2 • .: * . . . *

13

(CDC13 ), 65.93 (d of q, 1H), 5.44 (d of d, 1H), 1.79 (d of d, 3H), 1.62 (s,

3H); IR (ethyl ether) ve= o 1804cm -1 . Decoupling experiments show that the

vinylic resonances at 65.93 and 65.44 come from the different isomers of 3.

Integration of these absorptions shows that the cis and trans isomers of 3 are

present in approximately equivalent amounts.

Anal. Calcd for C7H804: C, 53.85; H, 5.13; Active Oxygen, 10.26; Molecu-

lar Weight, 156. Found: C, "3.85; H, 5.23; Active Oxygen, 9.77; Molecular

Weight (Osmometry), 162.

Ol1goeric Ester 4. Malonyl peroxide 3 (0.090g, O.58mmol) was added to

5OmL dry CH3 CN and the solution was heated at 840C for 14 h. The solution was

cooled and the solvent removed in vacuo to yield butenolide 3 (45% by GC) and

60mg (55% by weight) of 4: NMP (CDC 3), 65.86 (br, 2H), 1.79 (br, 3H), 1.55

(br, 3H); IR (CHCI 3)vco 1710cm-1.

Anal. Calcd for (C6 H8O)n: C, 64.28; H, 7.14. Found: C, 64.81; H, 7.70;

Molecular Weight (Osmometry) 550 (n - 5).

2,4-Dimethylbut-2-ent-4-olide 5. This compourd was prepared according to

the method of Gorewit and Rosenb um:8,17 bp 300C (0.07mm) (lit.8 300C

(O.05mm)); NMR (CDC 3) 67.05 (m, 1H), 4.90 (m, 1H), 1.93 (t, 3H), 1.40 (do 3H).

Acknowledgent: This work was supported by the Office of Naval Research.

~~~~~~.o.. o ° .. . . . . . . ..... , - . m . . . . .. .' '' ' b . .. * .. . . .

* 14

References

1. "Bioluminescence and Chemiluminescence", M. A. DeLuca and W. D. McElroy,

Eds., Academic Press, New York, 1981. "Chemical and Biological Generation

of Excited States", W. Adam and G. Cilento, Eds., Academic Press, New

York, 1982.

2. Schuster, G. B.; Schmidt, S. P. Adv. Phys. Org. Chem., 1982, 18, 187.

3. Koo, J.-Y.; Schuster, G. B. J. Am. Chem. Soc., 197T, 99, 6107.

* 14. Darmon, M. J.; Schuster, G. B. J. Org. Chem., 1982, 147, 4658.

5. Porter, J. E.; Schuster, G. B. J. Org. Chem., 1983, 48, 49144.

6. (a) Adam, W.; Rucktaschel, R. J. Am. Chem. Soc., 1971, 93, 557. (b) Adam,

W.; Rucktaschel, R. J. Org. Chem., 1978, 43, 3886. (c) Chapman, 0. L.;

Wojtkowski, P. W.; Adam, W.; Rodriguez, 0.; Rucktaschel, R. J. Am. Chem.

Soc., 1972, 914, 1365. (d) Adam, W.; Liu, J.-C.; Rodriguez, 0. J. Org.

Chem., 1973, 38, 2269.

7. Lucan, N. J.; Prater, A. N. J. Am. Chem. Soc., 1937, 59, 1682. Goldberg,

A. A.; Llnstead, R. P. J. Chem. Soo., 1928, 23143.

8. Gorewit, B.; Rosenblum, M. J. Org. Chem., 1973, 38. 2257.

9. Vassil'ev, R. F. Prog. React. Kinet., 1967, 14, 305.

10. Wilson, T.; Schaap, A. P. J. Am. Chem. Soc.. 1971, 93, 4126.

11. Benson, S. W. "Thermochemical Kinetics," 2nd ed.; Wiley: New York, 1976

*12. Schmidt, S. P.; Schuster, G. B. J. Am. Chem. Soc., 1980, 102, 7100.

13. Smith, J. P. ; Schrock, A. K. ; Schuster, G. B. J. Am. Chem. Soc., 1982,

104, 10141.

1J4. Dolby, L. J.; Riddle, G. N. J. Org. Chem., 1967, 32(1), 31481.

6-

15. Slougui, N.; Rousseau, G.; Conia, J.-M. Synthesis, 1982, 58.

16. Luoan, N. J. ; Prater, A. N. J. Am. Chem. Soc. 1937, 59, 1682. Goldberg,

A. A.; Linstead, R. P. J. Chem. Soc., 1928, 23 4l3.

17. Morel, T. H.; Verkade, P. E. Redl. Tray. Chem. Pays-Bas., 1949, 68, 619.

I 0

Table 1 -Kinetics of 3 Thermal Reactiona

Perylene (M) k~~(~)(Method)

4.7X10 1.6x10 (CIIL)b

6.3x1O _ 1.4x0 3 (CH-L)

6.3xlO ~ 1.2x10 3 (I)

9.4xlO- 2.3x1O-3 (CHL)

1.3x10-3 2.3x10-3 (CHL)

1.9x10-3 4.4x,0 3 (CHL)

3.BxI70 3 5.xIO-3 (CHL)

5.Ox10-3 9.7x10-3 (CHL)

k .OX1O-4 3- (IR); 6.OxlO-4s-' (CHL)

kA - 1.9 M-1s31 ( IR) ; 1 .6 M-'s-1 (CH-L)

aIn acetonitrile; 840C; 131 =8xlO1 M.

bCHL Indicates rate monitored by the decay

of the chemiluminescence.

dIR indicates rate measured by monitoring

the decay of the infrared absorption of 3.

J

Table 2. - Relative Chemiluminescence Yields.a

c

[31M ACTb lcorr

0.0100 Perylene 3.1 x 106

0.0080 2.6 x 106

0.0053 1.9 x 106

0.0040 1.3 x 106

0.0027 1.1 x 106

0.0020 7.8 x 105

0.001" 4.8 x 105

0.0010 2. x 105

0.0080 DPEA 1.5 x 106

0.0080 DPA 1.2 x 106

an acetonitrile; 340C

b[ACTI = 1.0 x 103 M

CTotal chemiluminescence intensity corrected for the

fluorescence efficiency of ACr in arbitrary units.

i :i : ; : " " " " " • . . . . ... . .. .. . "".

Table 3. - Temperature Dependence of the Thermal, Catalyzed, and

Chemiluminescent Reactions of 3a

(OC) k b - kdAT c (M-1s - I1 d

44 2.1 x 10- 4 0.12 465

54 2.2 x 10- 4 0.34 300

62 2.5 x 10- 4 0.56 950

74 3.6 x 10- 4 1.2 2200

84 5.7 x 10- 4 1.6 4225

94 1.8 x 10 2.1 8400

aIn acetonitrile containing 3 = 8 x 10-3 M,

bFrom the intercept of a plot of kobsd vs. perylene concentration; eq. 4.

cFrom the slope of a plot of kobsd vs. perylene concentration; eq. 4.

dInitial chemiluminescence intensity (before significant 3 is consumed in

arbitrary units.

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