Preparation and Properties of Benzotropones and Benzohomotropones

Western Michigan University ScholarWorks at WMU

Dissertations Graduate College

8-1979

Robert E. Suder Western Michigan University

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Recommended Citation Suder, Robert E., "Preparation and Properties of Benzotropones and Benzohomotropones" (1979). Dissertations. 2697. https://scholarworks.wmich.edu/dissertations/2697

This Dissertation-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Dissertations by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. PREPARATION AND PROPERTIES OF BENZOTROPONES AND BENZOHOMOTROPONES

Robert E. Suder

A Dissertation Submitted to the Faculty of The Graduate College in partial fulfillment • of the Degree of Doctor of Philosophy

Western Michigan University Kalamazoo, Michigan August 1979

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS

The author wishes to express his appreciation to Dr. Harmon, Dr. Iffland, Dr. Howell, Dr. Nagler, and Dr. Derby for allowing him to complete the degree. A special thanks goes to Dr. Harmon for his guidance,

inspiration, and incouragement. Invaluable assistance has come from the Department of Chemistry at Western Michigan University for the teaching associateship, and from the National Cancer

Foundation for the research fellowship.

Robert E . Suder

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Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. !5UDER» ROBERT EDWIN PREPARATION AND PROPERTIES OF BENZOTROPQNES AND BENZOHOHOTROPONES. WESTERN MICHIGAN UNIVERSITY. PH.D., 1979

Univt M. . International 300 n.zeeb road,ann arbor,mi w oe

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page

INTRODUCTION ...... 1 BACKGROUND ...... 3 Tropylium Ions ...... 3 Tropones and Benzotropones ...... 6 Homotropones and Homotropylium Ions ...... 7 DISCUSSION ...... 12

Polymethylenebenzotropones ...... 12 Bispolymethylenedibenzotropones ...... 18 Benzohomotropones ...... 25 Tropolone Derivatives ...... 31 EXPERIMENTAL ...... 34 Preparation of Benzotropones and Benzo- tropylium Ions ...... 34 Preparation of Bispolymethylenedibenzo- tropones ...... 49 Preparation of Benzohomotropones ...... 57 Preparation of Tropolone Derivatives ...... 62 CONCLUSION ...... 65 BIBLIOGRAPHY ...... 67

iii

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. INTRODUCTION

Interest in tropones (1) and tropolones {2) has

increased recently because many of their derivatives have been found to exist as natural products.

1 2

These include secondary vegetable metabolites such as stipitatonic (3.)1 and puberulic (^t)2 acids, as well

as sepedonin (5)-^

.OH .OHHO, H0-

.OH

HO ■CH. 5

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. A number of alkyl tropolones, such as nookatinol (6), Zj, have been found in the heartwood of various Cupressales.

Alkalodial tropolone derivatives, notably colchicine (2), have been found in plants of the lilacee.^

NHCOCH CH„0

Troponodial derivatives frequently show biological activity. One of the more interesting cases is the fungicidal activity of the tropolones of the Thu.ia

trees, which effectively preserve their wood.^ Also, antimiotic activity is found in various colchicine

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. BACKGROUND Tropylium Ions

In 1931 Huckel proposed that the tropylium ion, C^Hr7+, should possess aromatic character.® In fact,

the tropylium ion was prepared in I89I by M e r l i n g , ^

but was not identified. His work was repeated in 195^ and the yellow solid .that was isolated was proven to be tropylium bromide (8).10

n Br— /x^ vvvBr // \\

been able to prepare various types of tropylium salts by hydride exchange between cycloheptatrienes and tri-

(c 6h 5 )3c +y - (c6h 5)3c -h

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. A number of benzotropylium ions have also been prepared. The first isolation of one of these compounds lA was accomplished by Rennhard in 1955- He treated the benzotropone (£) with lithium aluminum hydride to afford the hydroxy compound (10), which upon addition of 70$ perchloric acid produced 11, a yellow solid.

LiAlHi

HClOi

One of the more extensively studied benzotropolone derivatives is that obtained from the methylation of the natural product purpurogallin (12), and this has led to the tropylium ion.

12 13

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 5 Eschenmoser. and’ coworkers were able to isolate the tropylium hexachloroplatinate salt (1^) by first reducing the carbonyl function of 12 with lithium aluminum hydride and then treating the resulting alcohol with hexachloroplatinic acid. ^

LiAlHi

The perchlorate salt has also been prepared using a similiar procedure. Proton NMR studies show the positive

charge is delocalized over both rings. The methoxyl protons in Ik are shifted about 2k Hz further downfield, compared to 12* This downfield chemical shift is attributed to the delocalized positive charge, which decreases electron density, decreasing shielding. ^

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Tropones and Benzotropones

On the basis of proton NMR studies, it can be concluded that tropone (1) is planar and has bond alteration.^ Also, the IR spectrum shows the carbonyl

absorption at 159^ cm-1, which is consistent for a conjugated system.1® Finally, the resonance stabilization energy of tropone is 1^ kcal mol ~1, whereas for cyclo- —1 19 heptatriene it is only 8 kcal mol . 7 X-ray crystallographic analysis of i|-,5-benzotropone (1^) show that it is almost planar, the carbonyl oxygen and the carbonyl carbon being displaced by 0.2 0 20 and 0.1 A, out of plane respectively. The IR carbonyl absorption is at 1590 cm-1, which is expected for a 21 conjugated ketone. Kloster-Jensen and coworkers were able to confirm that the tropone ring is reasonably planar by forcing the tropone ring out of planarity by a polymethylene bridge. A series of 6,8-polymethylenebenzotropones (16.) were prepared and it was found that the tropone ring is planar only if n ^ 7*21

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. (endo)H

It can be seen that the carbon-carbon -rr bond has been replaced by a methylene bridge forming a cyclopropane ring. Proton NMR studies of this compound clearly.in dicate the absence of any ring current.2^ The difference in the chemical shift between the endo and exo protons is only 0.5 Hz. The presence of a ring current would, of course, result in a greater difference in chemical shift of these protons, as seen in the case of the homotropylium ions. However, UV and IR spectra do seem to indicate a small contribution of the cyclopropane ring to electron 27 delocalization. Addition of perdeuterated sulfuric acid to 12 will form the substituted homotropylium ion (18).2^

(endo)Hv ,H(exo)

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 9 Proton NMR studies of the homotropylium ion (19) support the aromatic structure, and no cyclo propane ring is evident.^

(endo)R H(exo)

Protons H-^ and H2 exhibit a downfield shift to 6 6.62 due to the deshielding effect of the delocalized positive charge. If the cyclopropane ring remained intact, one would expect the signal to be at 6 7 or greater. Secondly, there is a large difference in the chemical shift of the endo and exo protons, with the endo proton at a much higher field than that of the exo

proton. The values are 6 -0.67 and 6 5*15 respectively. The increased shielding of the inside or endo proton can be attributed to the ring current of the homo tropylium ion.

Sugimura, et. al. prepared k,5-benzohomotropone (20) by treating 5-benzotropone (1 5) with dimethyloxosulfonium methylide (21) in tetrahydrofuran.^0

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0 15 + (CH3)2S=CH2 :0

21 20

Usually this ylide forms epoxides from carbonyl addition unless the carbanion intermediate can be stabilized by electron withdrawing groups, in which case cyclopropanation results. For example, the cyclopropanation of 15 proceeds slowly, but with the diester (22) it proceeds smoothly. -^0

Addition of perdeuterated sulfuric acid to 20 will form the corresponding substituted benzohomotropylium ion

(23).

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15 + DgSO^ ------>

A variety of homotropylium ions have "been prepared and all the evidence seems to indicate an aromatic

structure.

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The purpose of this work is to prepare a series of 6,8-polymethylenebenzotropones and 6,8-polymethylene- benzotropylium ions and then to determine the effect of the polymethylene bridge on the aromaticity of these compounds. Next, a series of 6,6':8,8°-bispoly-

methylenedibenzotropones and 6,6':8,8'-bispolymethylenedibenzotropylium ions were prepared and the physical

properties of these compounds were studied. Finally, two polymethylenebenzohomotropones and a benzohomotropylium ion were prepared. The effect of the poly methylene bridge on the aromaticity of these compounds

was investigated.

Polymethylenebenzotropones

Phthalaldehyde (2^) can be condensed with cyclic

ketones to give aldol-type condensation products, which dehydrate to form the 6,8-polymethylenebenzotropones

(25a-f) in 20-8*JfS yields.31,32

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Phthalaldehyde was prepared by treating a.a.a'.a'- tetrabromo-o-xylene with potassium oxalate.

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■CHBr,

+ 4 HBr

Cyclodecanone was prepared by the acyloin condensation of dimethylsebacate, followed by the reduction of the

hydroxy function.

C=0 h 3c o 2c (c h 2)8c o 2c h 3 + CH-OH

Zn/HCl

(c h 2)9 c =o

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Cyclotridecanone was prepared by first treating a-bromo- ethylacetate with cyclododecanone in the presence of zinc (Reformansky Reaction) to afford the hydroxy ester. The hydroxy ester was placed in an electrolysis cell and a current of 0.5 amp was passed for six hours, which produced the expanded cyclic ketone.

electrolysis oxidation

The dehydrated product, benzotropone (2^), was obtained in a single step for n ^ 7, whereas if n < 7 the adduct had to be treated with phosphorus pentoxide. As mentioned earlier, IR analysis indicated the tropone ring to be planar if n 7. Using proton NMR, it was possible to substantiate these views. For instance,

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in 2,7 - d i m e t h y l 5-benzotropone (2£)» the H& protons resonate at 6 7 *7 » which is consistent for a planar, conjugated system. H.

However, for 25a (n = 5) "the Ha protons resonate at 6 , 6.7 8, indicating that the tropone ring is not planar in this case. For 25d (n = 9), this resonance is at 6 7 .81. The downfield shift of the H& protons in the tropone ring can he attributed to the increased planarity of the ring system as the value of n is

increased. Also, the failure of the adduct 26a to dehydrate in the reaction mixture gives further evidence that the tropone ring is not planar if n < 7* One would expect rapid dehydration if a planar, conjugated

system were formed. Reduction of the carbonyl function with lithium aluminum hydride afforded the corresponding alcohols (28) in 60% yields. Usually the alcohols were isolated as oils which decomposed at room temperature.

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25 *

28a n = 5 28b n = 7 28c n = 8 28d n = 9 28e n = 10 28f n = 12

Treatment of the alcohols with an ether solution of 70$ perchloric acid gave the 6,8-polymethylene-4,5-benzo-

tropylium perchlorates (29). H

29a n = 10 29b n = 12

The proton NMR spectra of these compounds indicate a further downfield shift due to the deshielding effect of the delocalized positive charge. The H& protons now resonate at 6 9.2. This is consistent with the spectrum of tropylium hexafluorophosphate (4^) which shows a single, narrow signal at 6 9 .3.

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The perchlorates were isolated only if n = 10 or 12. Evidently, the slightest deviation in planarity of the tropone ring will inhibit the formation of the stable perchlorate salt. Perhaps the positive charge cannot be stabalized sufficiently if the ring system is not absolutely planar. The proton NMR spectra also indicates that the resonances of the aromatic protons are shifted downfield, from ca. 6 7.6 to 8.6, indicating that the positive

charge is delocalized over both rings.

Bispolymethylenedibenzotropones

To accomplish the synthesis of the 6,6':8,8'-

bispolymethylenedibenzotropones (jlO.)» the cyclic diketones (2!) were condensed with two mole equivalents of phthalaldehyde in the presence of methanolic sodium hydroxide. The products separated as colorless needles

in ^1-83f0 yields.

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Table I Physical Data of Benzotropones •H S o O H -P

n O O O VO VO VO VO vn vo CMCMCMCMCMCMCMCM

0 v 00 Ov 00 vo

xrv co co co co

vp\ M O VO VO CM cm

on n o

vo O n

*CD.,CN 19 CH0 - C=0 OCHO

31 n = 6,7,8,10

NaOH

30a n = 4 30b n = 5 30c n = 6 30d n = 8

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The cyclic diketones (21) were prepared from the corresponding diacid- chlorides (32.) hy the procedure as reported "by Blomquist et.al.J

Et«N 2 Cl'0C(CH2)nC0Cl — X > 6 6

32a n = 6 32b n = 7 32c n = 8 32d n = 10 31a n = 6 31b n = 7 31c n = 8 31d n = 10

The IR spectra of the bisbenzotropones show the

carbonyl absorption at 1595 - 1605 cm-1, suggesting that the tropone ring is planar. As indicated earlier, when the tropone ring is non-planar, electronic delocalization is inhibited and the carbonyl absorption appears at 1650 - 1700 cm-1. The proton NMR spectrum indicates a planar tropone ring. The H& protons resonate

at 6 7 .0-7 .^, which is consistent for a conjugated system. Recall that the H& protons will resonate at 6 6 .7 8 for a non-planar tropone.

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Lithium aluminum hydride reduction of 30 afforded the

corresponding dihydroxy compounds (33.), isolated as oils, in 60fo yields. These compounds were unstable and quickly decomposed at room temperature. The dihydroxy compound 33a was treated with an ether solution of 70$ perchloric acid to afford the crystalline 6,6':8,8*- ■bispolymethylenedibenzotropylium perchlorate (3^-).

30a

OH HO,

33a

HCIO^ V

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The perchlorate was isolated as red crystals in a 50$ yield. This compound is an interesting example of a substance containing two positive charges within the

same molecule. It proved impossible to convert the diketones 30b-d into the corresponding bisbenzotropylium perchlorates because of the poor solubility of the former.

Elemental analysis of the perchlorate salt indicated the presence of two units of acetic acid incor porated in crystallization; this was substantiated by the presence of a sharp carbonyl absorption at 1710 cm-"*' in the IR spectrum. The NMR spectrum was not obtainable

because a suitable solvent could not be found. The UV spectrum (98$ HgSO^) gave a sharp absorption maxima at 29^ nm, which is consistent with benzotropylium

perchlorate (282 nm).^2’^

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. oduced ih r si ft opyrght wnr Furhe r oduci r bie tot r si . n issio erm p ithout w ited ib h pro n ctio u d ro p re er rth u F ner. ow t h rig y p co e th of n issio erm p with d e c u d ro p e R

Physical Data of Bisbenzotropones £-5cS •H ^s P H O O O H ■P ^ e P - w A 0 «H o 0 0 p

A > O vo lO U> >A T V\ \ V VT\ 0 * O n s O O O O VO VO M M CM CM CM O n O XT\ 2k 25

Benzohomotropones

The preparation of the bridged benzohomotropone was made according to the general procedure of Sugimura, et. al.-^ Addition of a tetrahydrofuran solution of dimethyloxosulphonium methylide to a well stirred solution of the ketone (2 5d) under nitrogen at 0° afforded a white solid, identified as la,3-nonamethylene-

benzohomotropone (.25) •

(CH0)0S=CH

(endo) „H(exo)

The IR spectrum shows the carbonyl absorption at 1640 cm-1, indicating a loss of partial conjugation because the atoms are not coplanar. Interpretation of the proton NMR spectrum is more difficult because the absorption band of the cyclopropyl protons lie hidden under the

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 2 6

methylene protons. For example, the endo and exo

protons in benzohomotropone (,3J5) reasonate at 6 I .76 and 1.88 respectively.

exo)

This is also the region where the methylene protons absorb for 35* However, it can be observed that for 36 the H& protons absorb at 6 6.6. and the aromatic

protons at 6 7 .1 -7 .^. This is consistent with the fact that the cyclopropane ring will inhibit conjugation. Otherwise, the H& proton would be expected to resonate

at ca. 6 7*3* The polymethylene benzohomotropone is very stable

and can be stored indefinitely. Usually sulfur ylide addition would result in epoxidation. However, in this case the carbonyl function is hindered by the methylene bridge. Even the cyclopropanation preceeds slowly because of the inductive de- stabalizing effect of the a-alkyl group on the developing negative charge.

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Addition of perdeuterated sulfuric acid produced a

green solution, the benzohomotropylium ion (37).

endo

Compound 22 was very unstable and the proton NMR spectrum had to be obtained immediately. The aromatic protons still resonate at 6 7 .1 -7 .^, indicating that the positive charge is not delocalized over both rings, as is the case for benzotropylium ions. The delocalized positive charge on the homotropone ring caused the H&

proton to resonate at 6 7 *^ which is to be expected due to the completely delocalized positive charge. The ring current caused the endo proton absorption to be shifted

upfield to 6 -O.3 5. Again, this is consistent with other homotropylium ions. Attempts to prepare the homotropone from 25f (n = 12) were unsuccessful. The methods of both Sugimura and Paquette were failures. ^ Molecular models of compound 25f seem to suggest that the methylene bridge is capable of folding back over the ring, effectively preventing the dimethyloxosulphonium-

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table III Physical Data of Benzohomotropones

NMR

compound 35 compound 37 A 6 assignment (c d c i 3) (B2S°k ) 21 - 21

endo H 1.8* -0.35 +2 .2 exo H 1.9* 2.8* -0 .9

Ha 6.6 7.4 -0 .8 aromatic 7.1 - 7.^ 7.1 - 7.^ 0

^estimated value - proton hidden under methylenes

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methylide from attacking the double bond. Preparation

of the bishomotropone from 30a and 30b were likewise unsuccessful. Molecular models may provide some insight

here also. It appears that the carbonyl oxygen atoms

are in very close proximity to each other if both benzotropone rings lie on the same plane. A more stable and less hindered conformation would result if the benzotropone rings lie one over the other. This con formation may prevent the attacking dimethyloxosulfonium methylide from•approaching the double bond. For the case of 25d (n = 9) where cyclopropanation did occur, models indicate that the methylene bridge lies on the same plane as the benzotropone ring, making nucleophilic attack on the carbon-carbon double bond relatively unhindered. The addition of dimethyloxosulfonium methylide to

25a (n = 5) seems to result in both epoxidation and cyclopropanation. First, the carbonyl absorption in the IR spectrum disappeared and was replaced by an absorption at 1180 cm-1 which suggests the epoxide. The proton NMR spectrum also indicates structure 28. The H& protons

have disappeared and replaced by peaks at 6 3 .2 and 3.3, which may be the cyclopropyl protons.

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It is rather suprising that 38 would form because with a,P unsaturated ketones, usually cyclopropanation results. Molecular models show that the methylene bridge cannot interconvert conformations from one side of the tropone ring to the other. It actually stays over the tropone ring as shown in 39.

This leaves the carbonyl unhindered and epoxidation can

result.

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Tropolone Derivatives

Tropolone (2) was obtained by the ring enlarge

ment of 7, 7-dichlorobicycloC3.2.0]hept-2-en-6-one (32.) • 0

f > Y coi . ^ ' C i . o HOAc(aq) ^ \ — /

39 2

Proton NMR data indicate extensive intramolecular hydrogen bonding for tropolone. The hydroxyl resonance

appears at 6 9 -5 1, which is consistent for a hydrogen bonded structure. Also changing the concentration of the solvent does not affect the OH stretching frequency

in the IR spectrum. 4,5-benzotropolone (40) was prepared in a similiar manner using 2,3-benzo-7,7-dichlorobicycloC3.2.0]heptan-

6-one (41).

Cl Cl

o r HOAc(aq) 41

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Again, spectral data indicates extensive intramolecular

hydrogen bonding. ^,5-Benzotropolone is readily methylated by treat

ment with dimethylsulfate.

1+2

As expected, the spectrum of j+2 is similiar to benzo

tropone s. The spectra of tropolone and 1+,5-benzotropolone were used as comparisons for the bridged benzotropones.

Table IV Physical Data of Tropolone Derivatives 33 EXPERIMENTAL

All melting points reported are corrected and expressed in degrees Celsius. The ultraviolet spectra were obtained with a Cary model 1^ spectrophotometer. The infrared spectra were measured with a Beckman IR-8 instrument. The nuclear magnetic resonance spectra were obtained with a Varian A-60 instrument; resonances were measured in Hz downfield from a tetramethylsilane internal standard. Thin- layer chromatography was performed on silica gel-G using heptane as the solvent. The spots were developed by iodine vapor. Elemental analyses were preformed by Galbraith Microanalytical Laboratories, Knoxville, Tennessee. The acids, cyclic ketones, and the a,a,a',a'-tetrabromo-o-xylene were obtained commercially, except where noted.

Preparation of Benzotropones and Benzotropylium Ions

The 6,8-polymethylenebenzotropones were prepared 21 according to the general procedure of Kloster-Jensen. o-Phthalaldehvde 2^37

A solution containing 250 g (0.59 mol) of cl,cl,a.',cl' - tetrabromo-o-xylene, 221 g (1.2 mol) of potassium oxalate 3k

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monohydrate, 1.4- L of water, and 1.4 L of ethyl alcohol was stirred vigorously and heated at reflux temperatures for 50 hours. At the end of this time, the ethanol was largely removed by distillation and 450 g of disodium hydrogen phosphate dodecahydrate was added. The mixture was steam distilled until 9 L of distillate was obtained.

The distillate was saturated with sodium sulfate and extracted with ethyl acetate. The extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was crystallized from 90 - 100° ligroin, and a second crop obtained by concentration of the mother liquor. The total yield of o-phthalaldehyde was 47*1 g (59$)» m.p. 54-55° (lit.-^

55-5-56°).

6.8 Pentamethvlene-5-hvdroxybenzotropone 26a A solution containing 1.3 g (0.01 mol) of

phthalaldehyde, 1.3 g (0.01 mol) of cyclooctanone, 300 ml of ethyl alcohol, and 60 ml of saturated sodium hydroxide/methanol was heated at reflux for lj hours. The solvent was removed under reduced pressure and water was added to the residue. This residue was extracted

with ether and dried with anhydrous magnesium sulfate. After filtration, the solvent was removed under reduced pressure to give a white solid which was crystallized from methanol to yield 1.2 g (50^); m.p. I65-I670

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(lit. 21 169-170 °).

6.8-Pentamethvlenebenzotronone 26a In a flask equipped with a calcium chloride drying tube and an efficient stirrer was placed 0 .7 g (0.0029 mol) of the alcohol 26a . 0 .8 g (0.0056 mol) of phosphorus pentoxide, and 50 ml of anhydrous benzene. After being heated at reflux for two hours, the mixture was filtered and the solvent removed under reduced pressure. The residue was crystallized from ether/30-

6 0 0 petroleum ether to give 0 .2 5 g (38$) of white crystals; m.p. 128-129° (lit.21 132-133°); NMR(CDC13) 6 0.9-2.3 (m, 10H, (CHg)^), 6 .7 8 (d, 2H, J=2 Hz, H&), 7.05-7.60 (m, 4H, ArH); IR(Nujol) 1679 (C=0) and 1618 (C=C) cm"1 .

6 .8-PentaTnethylenebenzocyclohenten-7-ol 28a A suspension containing 0 .3 g (0.0013 mol) of 6 .8-penthamethylenebenzotropone (25a). 0.2 g (0 .0 0 5 mol) of lithium aluminum hydride, and 10 ml of anhydrous ether was stirred for 3 hours at 0° and for 3 hours at room temperature. Water was then added slowly to decompose the excess lithium aluminum hydride. The

mixture was filtered and the ether layer separated, dried over anhydrous magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure. An oil, presumed to be the alcohol, remained. IR analysis

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indicated the loss of the carbonyl absorption and the

presence of a hydroxyl band, centered at 3350 cm -1. The hydroxy compound was unstable and decomposed readily. It decolorized readily at room temperature.

Attempted synthesis of 6.8-pentamethylenebenzotropylium perchlorate An excess of 70$ perchloric acid was added to 0.2 g (0.0 0 0 8 mol) of the hydroxy compound 28a in 10 ml of ether. The ether layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated by reduced pressure to give an oil, identical to the starting.material. This was confirmed by TLC.

Dimethylsebacate A solution containing 30 g (0.15 mol) of sebacic acid, 100 ml (2 .5 mol) of methanol, and 6 ml of con centrated hydrochloric acid was heated at reflux for three hours. After the addition of 100 ml of water, the

solution was extracted with benzene. The benzene solution was washed with water and then with a 10$ sodium carbonate solution. The benzene solution was then dried over anhydrous magnesium sulfate, filtered,

and evaporated under reduced pressure. The residue was purified by distillation to give 2 6 .3 g (77 $); b.p. 135°/l mm (lit.**'1 1 7 5 °/2 0 mm).

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2-Hydroxycyclodecanone (acyloin condensation)

Over a perio'd of 23 hours, 23*4 g (0.12 mol) of dimethylsebacate in 250 ml of xylene was added to 23 g (0.44 mol) of 40$ sodium dispersion in 1 litre of

xylene. A high speed stirrer was necessary to keep the mixture in suspension. During the addition, the mixture was under a nitrogen atmosphere and heated to reflux temperature. After refluxing for one additional hour, the reaction mixture was cooled in an ice hath, and 35 ml of glacial acetic acid was added slowly, followed by 125 ml of water. The mixture was filtered and the aqueous layer separated. This layer was extracted with xylene. The combined xylene fractions were dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure. The residue was purified by distillation to give 8.0 g (42$) of the hydroxy ketone;

b.p. 124-129°/8 mm (lit.**'2 110-115°/0.1 mm).

Cvclodecanone Eighteen millilitres of concentrated hydrochloric

acid was added to a well stirred solution containing 8.0 g (0.047 mol) of 2-hydroxycyclodecanone, 9 g of zinc dust, and 20 ml of glacial acetic acid. The mixture was heated at 75-80° for l^ hours; two additional

18 ml portions of hydrochloric acid were added at 30 minute intervals. The mixture was allowed to cool, and

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 39

180 ml of a saturated aqueous sodium chloride solution was added. The mixture was extracted with ether, and the non aqueous layer washed with a 10$ aqueous sodium carbonate solution and then with water. The ether

solution was dried over anhydrous magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure. The residue was distilled to give 5*2 g

(72$) of the ketone; b.p. 100-102°/l2 mm (lit.**’3 100- 1 1 5 °/1 2 mm).

6.8-Hentamethvlenebenzotronone 25b A solution containing 1.3^ g (0.01 mol) of

phthalaldehyde, 1 .5^ g (0 .0 1 mol) of cyclodecanone, 60 ml of saturated methanoic sodium hydroxide, and 300 ml of ethanol was heated at reflux temperature for l|- hours. The solvent was removed by evaporation under reduced pressure. Water was then added to the residue and extracted with ether. The ether was dried with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was crystallized from a mixture of ether/30-60 0 petroleum ether to give

1 .5 g (60$) of colorless needles; m.p. 107 -108° (lit. 21 110-111°); NMR CDC13 6 1.0-3.7 (m, 14H, (CH2)?), 7-2 (s, 2H, Ha ), 7.48 (d, 4-H, j = 2 Hz, ArH); IR(Nujol) 1609 (C=0) and 1623 (C=C) cm"1 .

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 6.8-Heptamethvlenebenzocvclohepten-7-ol 28b A mixture containing 0.^ g (0.0015 mol) of 6.8-heptamethylenebenzotropone (25b). 0 .5 5 g (0 .1 5 mol)

of lithium aluminum hydride, and 10 ml of anhydrous ether was stirred for three hours at 5° and for three hours at room temperature. Water was then added slowly, decomposing the excess lithium aluminum hydride. The solution was filtered and the ether layer separated. It was dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure to give an oil. The IR spectrum suggested the oil to be the expected hydroxy compound because of the absorption at 3300 cm 1 and the

disappearance of the carbonyl peak. This oil was unstable and decomposed at room temperature because it

decolorized rapidly.

Attempted synthesis of 6.8-heptamethvlenebenzotropylium perchlorate An excess of 709S perchloric acid was added to 0.1 g (0 .OOOtt mol) of the oil 6,8-heptamethylenebenzocyclo- hepten-7-ol (28b) dissolved in 15 ml of ether. After separation of the ether layer, it was concentrated under

reduced pressure to give an oil, identical to the starting material as confirmed by TLC.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 6.8-Nonamethylenebenzotro-pone 25d

A solution containing 1.34 g (0.01 mol) of phthalaldehyde, 1 .8 2 g (0 .0 1 mol) of cyclododecanone, 300 ml of ethyl alcohol, and 50 ml of saturated sodium

hydroxide in methanol was heated at reflux for hours. The solvent was then removed under reduced pressure and 100 ml of water added to the residue. The mixture was extracted with ether, filtered, and evaporated under reduced pressure. The residue was crystallized from a water/methanol solution to yield 2 .3 g (78%) of white

needles; m.p. 115-116° (lit. 21 116-117°); NMR (CDC13) 6 O.9-3 . 8 (m, 18H, (CH2)9), 7.31 (d, 2H, J = 3 Hz, H& ), 7.48 (d, 4H, J = 3 Hz, ArH); IR(Nujol) 1610 (C=0) and 1623 (C=C) cm-1.

6.8-Nonamethvlenebenzocvclohepten-7-ol 28d A suspension containing 1.0 g (0.0035 mol) of

6.8-nonamethylenehenzotropolone (25d). 0.25 g (0.057 mol) of lithium aluminum hydride, and 20 ml of anhydrous ether was stirred for three hours at 5° and for three hours at room temperature. A 10% aqueous ammonium

chloride solution was added slowly and the mixture stirred for 30 minutes. The ether layer was separated, dried over anhydrous magnesium sulfate, and evaporated under diminished pressure to afford 0 .5 g (50%) of the alcohol as colorless crystals (from 30-60° petroleum

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 42

ether); m.p. 88-8 9.5°; NMR (CDCl^) 6 O.9-3.I (m, 18H,

(CH2)9), 4.1 (s, 1H, OH), 6.25 (s, 2H , Ha), ?.l5 (s, 4H, ArH); IR(Nujol) 3580 (OH) and 1640 (C=C) cm-1.

Anal. Calcd. for ^2^ Z 6 0t 85*lj H ’ 9 ‘20, Found C, 84.96; H, 9-15*

Attempted synthesis of 6.8-nonamethylenehenzotropylium perchlorate An excess of 70fo perchloric acid was added to 0 .2 g (0.0 0 0 7 mol) of 6,8-nonamethylenebenzocyclohepten-

7-ol (28d) dissolved in 10 ml of ether. The layers were separated and the ether portion was dried over magnesium sulfate, filtered, and evaporated under diminished press ure to give the starting material, as confirmed by TLC.

Attempted synthesis of 6.8-nonamethvlenebenzotropvlium hexachloroplatanate A solution containing 0.5 g (0.0018 mol) of 6,8- nonamethylenebenzocyclohepten-7 -ol (28d) in 20 ml of ether and 0 .5 g (0 .0009 mol) of hexachloroplatinic acid hexahydrate in 50 ml of ether was stirred for one hour. At the end of this time, the solution was filtered and the solvent removed by evaporation under reduced pressure. Only starting material was recovered, as

indicated by TLC.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ^3

Ethvl-2-hydroxycyclododecanecarboxylate (Reformansky) Two hundred millilitres of anhydrous benzene, 200 ml of anhydrous toluene, and 9*8 g of zinc were heated to reflux temperature. To this solution was added 25 g

(0 .1 5 mol) of ethyl bromoacetate and 25 g (0 .1 3 mol) of cyclododecanone in 80 ml of benzene. The addition was accomplished over a period of two hours. After further refluxing for two more hours, the mixture was cooled in

an ice bath and 110 ml of 30$ sulfuric acid added. After filtration, extraction with benzene, and evapora tion, and oil was obtained, presumably the hydroxy ester. It was used without purification for the next step.

2-Hydroxycyclododecanecarboxylic acid

A mixture of 15 g (0.06 mol) of crude ethyl-2- hydroxycyclododecanecarboxylate and 25 g of sodium

hydroxide in 100 ml of water was heated at 65° for four hours. This mixture was cooled in an ice bath and treated with a 1:1 aqueous hydrochloric acid solution until acidic to congo red. The white solid was collected and crystallized from benzene to give 11 g (80$) of product; m.p. 139-140° (lit.^ 141-142°).

Cyclotridecanone (method of Sharkey-^) Ten grams of 2-hydroxycyclododecanecarboxylic acid,

100 ml of acetonitrile, and 3 ml of triethylamine were placed in an electrolysis vessel, equipped with a

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platinum anode. The carbon cathode was placed in a porous ceramic cup which was filled with 2 N potassium hydroxide in methanol. A current of 0.5 amps at 137 volts was passed for 17 hours. The temperature was maintained at

approximately 15°• The mixture was filtered and extracted with ether. The extract was dried over anhydrous mag

nesium sulfate, filtered, and evaporated to give a residue which was purified by distillation to give I .63 g (20$) of the ketone; b.p. 13 0-132°/8mm (lit. 38 138°/l2 mm).

6.8-Decamethvlenebenzotro-pone (25e) A solution containing 1.13 g (0.0084- mol) of

phthalaldehyde, I .63 g (0.0084- mol) of cyclotridecanone, 250 ml of ethanol, and $0 ml of saturated sodium hydroxide in methanol was heated at reflux temperature for three hours. The solvent was then evaporated, and 250 ml of water was added. The mixture was extracted with ether, and the ether solution was dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure. The residue was crystallized from 30-60° petroleum ether

to give 0 .8 g (32$) of white crystals; m.p. 92-9 2.5°; NMR(CDC13) 6 1.1-3.0 (m, 20H, (CH2)10), 7*27 (s, 2H, H& ), 7.4-4- (d, 4-H, J = 2 Hz, ArH); IR(Nujol) 1610 (C=0) and 1620 (C=C) cm"1 .

Anal. Calcd. for C2iH260: C, 85.7; H, 8.8 5. Found: C, 8 5.7 6; H, 8.91.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 6.8-Decamethvlenebenzocyclohepten-7-ol 28e A suspension of 0 .3 g (0.0015 mol) of 6,8-

decamethylenebenzotropone (26e), 0 .2 g of lithium aluminum hydride, and 15 ml of anhydrous ether was stirred for one hour at 10° and for three hours at room temperature. A 10% aqueous ammonium chloride solution was added slowly. The ether layer was separated, dried over anhydrous magnesium sulfate, and evaporated under diminished pressure to give 0 .2 g (66%) of an oil, presumed to he the alcohol (28e). The IR spectrum indicated the loss of the carbonyl group and the appearance of a new band centered at 33*1-0 cm “1, which corresponds to the hydroxyl group.

6.8-Decamethvlenebenzotropylium perchlorate 29a An excess of 70% perchloric acid was added to a solution containing 0 .2 g (0 .0 0 1 1 mol) of 6,8-deca- methylenecyclohepten-7-ol in 20 ml of ether. Yellow crystals began to appear at once. They were crystallized from glacial acetic acid to give 0.15 g of product (40%);

m.p. 163-165°; NMR (CH3CN) 6 O.8-3 .6 (m, 20H,(CH2)10), 8.36-9.30 (m, 4H, ArH), 9*52-9.70 (m, 2H, H& ); IR(Nujol) 1590 (C=C) cm-1; UV (95% HgSO^) 291 (^55,000); 3*1-8 (6 3900); and 440 (€2000) nm. Anal. Calcd for C^H^CIO^: C, 6 6.8; H, 7-14;

Cl, 9.83* Found:C, 66.62; H, 7.23, Cl, 9.65*

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6.8-Dodecamethvlenebenzotro-pone 25f A solution containing 1.34 g (0.01 mol) of phthalaldehyde, 2.24 g (0.01 mol) of cyclopentadecanone,

300 ml of ethanol, and 50 ml of saturated sodium hydroxide in methanol was heated at reflux for 1-g- hours. The solvent was then removed by reduced pressure and water added. The mixture was extracted with ether. The ether was dried over anhydrous magnesium sulfate, filtered, and evaporated under diminished pressure. The residue was crystallized from water/methanol to give 2.7 g (8tyfo) of product; m.p. 64-66° (lit.^1 65-66°); NMR (CDC13) 6 1.1-3.0 (m, 24H, (CH2)12), 7-52 (s, 2H, H&) 7.6 (d, 4H, J = 4 Hz, ArH); IR(Nujol) 1590 (C=0) and

1615 (C=C) cm"1 .

6.8-Dodecamethvlenebenzocyclohenten-7-ol 28f A suspension of 0.4 g (0.0012 mol) of 6,8- dodecamethylenebenzotropone (25f). 0.2 g (0 .0 0 5 mol) of lithium aluminum hydride, and 20 ml of anhydrous ether was stirred for three hours at 5° and for three hours at room temperature. Water was slowly added, the layers separated, the ether layer dried, filtered, and evaporated under reduced pressure to give an oil, presumed to be the alcohol 28f. The IR spectrum

shows the absence of the carbonyl absorption and a new band at 3510 cm"1, corresponding to the hydroxyl group.

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6.8-Dodecamethvlenebenzotropylium perchlorate 29h An excess of 709S perchloric acid was added to 0 .3 g

(0 .0009 mol) of 6,8-dodecamethylenebenzocyclohepten-7- ol in 15 ml of ether. The yellow crystals that formed were recrystallized from glacial acetic acid to give

0.3 g (80$) of product; m.p. 170-171°; NMlUCD^CN) 6 0.8- 3.6 (m, 24-H, (CH2)12), 8.3 6-9 .2 0 (m, 4-H, ArH), 9*64- (d, 2H, J = 4- Hz, H ); IR(Nujol) 1590 (C=C) cm-1; UV (98$ H2S0^) 292 (£6 0,000), 349 (£50 0 0), 4-50 (f 1800) nm. Anal, calcd. for C^H^CIO^: C, 6 7.9; H, 7•6 6; Cl, 8.73. Found: C, 68.02; H, 7.64-; Cl, 9*01.

6.8-Dimethylhenzotropone 27 A solution containing 0.5 g (O.OO37 mol) of phthalaldehyde, 0 .3*1- g of diethyl ketone (0.004- mol), 200 ml of ethanol, and 25 ml of saturated sodium hydroxide in methanol was heated at reflux for three hours. The solvent was removed under reduced pressure and 100 ml of water added. The mixture was extracted with ether, and the ether layer dried over anhydrous magnesium sulfate. After filtration, the ether was evaporated under reduced pressure to give a residue

which was crystallized from cyclohexane to give 0 .5 g (75$) of product; m.p. 85-86° (lit.21 86-87°); NMR (CDCl^) 6 2.32 (s, 6H, CH3), 7-68 (d, 4-H, ArH), 7*70 (s, 2H, Ha ); IR(Nujol) 1596 (C=0) and 1616 (C=C) cm”1 .

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6.8-Octamethvlene'benzotropone 25c A solution containing 1.34 g (0.01 mol) of phthalaldehyde, 1.68 g (0.01 mol) of cycloundecanone,

200 ml of ethyl alcohol, and 50 ml of methanoic sodium

hydroxide was heated at reflux temperature for two hours. The solvent was removed under reduced pressure and water added to the residue. The mixture was extracted with ether, and the ether layer was dried over anhydrous magnesium sulfate, filtered, and evaporated at reduced pressure to give 1.0 g (38$) of white crystals (from

ether); m.p. 126-127° (lit.21 126-127°; M R (CDCl^) 6 0.9-3.7 (m, 16H, (CH2 ) q), 7.38 (d, 2H, Ha ), 7-59 (d, 4H, ArH); IR(Nujol) 1604 (C=0) and 1616 (C=C) cm"1 .

6.8-0ctamethvlenehenzocvclohenten-7-ol 28c A suspension of 0.5 g (0.002 mol) of 6,8-octa- methylenehenzotropone and 0.5 g (0 .0 1 3 mol) of lithium aluminum hydride and 15 ml of anhydrous ether was stirred for one hour at 5° and three hours at room temperature. A 10fo aqueous ammonium chloride solution was added slowly, the layers separated, the ether layer

dried over anhydrous magnesium sulfate, filtered, and evaporated to give 0 .3 g (60$) of an oil. This oil was presumed to be the alcohol on the basis of IR spectrum analysis: the carbonyl absorption disappeared and a new band centered at 3380 cm"1 appeared.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Attempted synthesis of 6.8-octamethylenebenzotropylium perchlorate An excess of 70 fo perchloric acid was added to 0 .3 g (0 .0 0 1 1 mol) of 6,8-octamethylenebenzocyclohepten-7 -ol in 8 ml of ether. The ether layer was separated, dried, and concentrated under reduced pressure to give an oil, which TIC indicated to he identical to the starting alcohol.

Tropyliumhexafluorophosphate 4313 A solution containing O.92 g (0.01 mol) of 1,3>5“ cycloheptatriene, 3*9 g (0 .0 1 mol) of triphenylmethyl hexafluorophosphate, and 60 ml of methylene chloride was stirred for five minutes. The solid was collected to give 1 .8 g (76$) of pure yellow crystals; m.p. 186-187°

(lit. 13 187-188°); NMR (CD^CN) 6 9 .3 (s, 7H).

Preparation of Bispolymethylenedibenzotropones

33 The general procedure of Blomquist, et. al.was used to prepare the diketones. The acid chlorides were Ck prepared by the method of Cason.

Suberoyl Dichloride A mixture of 3^.8 g (0.2 mol) of suberic acid, and 90 g (O.7 5 mol) of thionyl chloride was heated for 21 hours at 50°. The unreacted thionyl chloride was removed under reduced pressure, and the residue purified

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by distillation to give 36 g (93%) °f the dichlorides b.p. 137-1390/! mm (lit.2*5 l62-l63°/l5 mm).

1.7-Cyclotetradecadione 31a Over a period of 3i hours, a solution of 3 5 .9 g (0 .1 7 mol) of suberoyl chloride in 300 ml of anhydrous benzene was added to a refluxing solution containing

four litres of benzene and 250 ml of triethylamine, previously dried over sodium hydroxide. The mixture was

allowed to reflux for an additional three hours. The mixture was filtered, and the benzene distilled under reduced pressure. The residue was cooled to 0° and 25 g of potassium hydroxide in 100 ml of methanol was added slowly. The solution was again heated to reflux tempera ture for one hour. Then 100 ml of water was added and the mixture heated at reflux for two hours. At the end of this time, the methanol was distilled under reduced pressure, and the aqueous mixture extracted with ether. The ether was dried over anhydrous magnesium chloride, filtered, and removed under diminished pressure. The residue was crystallized from 2-propanol to give 0.42 g (2.2%) of gold plates; m.p. 145-146° (lit.^ 146-147°).

6 .6 *:8.8'-Bistetramethvlenedibenzotropone 30a A solution containing 0.54 g (0.004 mol) of phthalaldehyde, 0.42 g (0 .0 0 1 9.mol) of 1 ,7 -cyclo-

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tetradecadione (31a), 150 ml of ethanol, and 50 ml of saturated sodium hydroxide in methanol was heated at reflux temperature for hours. The solid that formed was collected and crystallized from tetrahydrofuran to

yield 0 .7 g (83$) of a white solid; m.p. 347-350°; NMR

(CD3CN) 6 1.2-2.9 (m, 16H , (CH2)q), 7-0 (s, 4H, H&), 7.2-7.6 (m, 8H, ArH); IR(Nujol)1595 (C=0) and 1623 (C=C) cm-1; UV (98$ H2S0^) 236 (£50,200), 264 (€40,300),

342 (€307 0), and 359 (€1 7 0 0 ) nm.

Anal. Calcd. for ^ ^ 2Q°2: Cf 85’7i H> 6#4, Found: C, 8 5.6 5, H, 6.6.

6.6* : 8. 8 1-Bistetramethvlenedibenzocvclohe'pten-7-ol 33 A suspension of 0.55 g (0.013 mol) of 6,6': 8,8’-bistetramethylenedibenzotropone (30a ) and 0 .3 g (0.0 0 8 mol) of lithium aluminum hydride in 200 ml of anhydrous tetrahydrofuran was stirred for three hours at 0° and for three hours at room temperature. The excess lithium aluminum hydride was decomposed by the slow addition of water. The mixture was evaporated under reduced pressure to give 0.4 g (73$) of an oil. This oil was presumed to be the alcohol because the IR spectrum indicates the disappearance of the carbonyl absorption and the presence of a band centered at 3300 cm-1. This oil decolorized readily, showing it to be unstable at room temperature.

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6,61;8.8 *-Bistetramethylenedibenzotropylium perchlorate 3k An excess of 70% perchloric acid was added to 0.4 g (0.001 mol) of 6,6' :8,8'-histetramethylene- dibenzocyclohepten-7-01 (33_). Bright yellow crystals formed immediately. They were collected and crystal lized from an acetic acid/acetonitrile mixture to give 0.45 g of the product (81$); m.p. 237°(explodes); UV (98% H2S0^) 246 (687,700), 294 (6212,000), 348 (617,800), 361 (6 5930), and 450 (65900) nm; IR(Nujol) 1710 (AcOH) cm"1 .

Anal. Calcd. for C ^ H ^ C l g O g ^ CHyJOOH: C,57*75; H,

5.45? Cl, 10.25. Found: C, 57-75; H, 5-35; Cl, 10.05.

Azelaovl dichloride A mixture of 37*6 g (0.2 mol) of azelaic acid and 90 g (O.75 mol) of thionyl chloride was heated at 50° for one day. The excess thionyl chloride was removed under reduced pressure and the residue

distilled to give 37*9 g (84%) of the dichloride; b.p. 143-145/9 mm (lit. ^ 166/18 mm).

1.8-Cvclohexadecadione 31b Over a period of three hours, 37*9 g (0.17 mol) of azelaoyl dichloride in 300 ml of anhydrous benzene

was added to a solution containing 3*75 L of refluxing benzene and 245 ml of triethylamine (dried over sodium

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hydroxide). The mixture was stirred for an additional three hours. After standing overnight, the mixture was filtered to remove the triethylamine hydrochloride. Then the henzene was distilled under reduced pressure.

The residue was cooled to 0° and 25 g of potassium hydroxide in 100 ml of ethanol was added slowly. The solution was heated at reflux for one hour. Then 100 ml of water was added and the solution refluxed for another two hours. The ethanol was removed by distillation under reduced pressure and the residue extracted with ether. The ether was dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure. The residue was crystallized from 2-propanol to give 6.4 g

(30$) of the diketonej m.p. 64-65° (lit.^ 67-68°).

6.6 ? S 8.81-Bisoentamethvlenedibenzotropone 30b One gram of 1,8-cyclohexadecadione (0.004 mol), 1 .0 5 g (0.008 mol) of phthalaldehyde, and 200 ml of ethanol were heated at reflux in the presence of 100 ml of a saturated solution of sodium hydroxide in methanol for lj hours. The solvent was removed by distillation

under diminished pressure, and 100 ml of water added to the residue. The mixture was extracted with ether, the ether layer dried over anhydrous magnesium sulfate, and filtered. The ether was removed under reduced pressure. The residue was crystallized from tetrahydrofuran to

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give O .95 g (54$) of product; m.p. 265-266°; NMR (CD^CN)

6 1.0-2.9 (m, 20H, (CH2)10), 7-1 (s, 4H, H&), 7-5-7.7 (m, 8H, ArH); IR(Nujol) 1595 (C=0) and 1623 (C=C) cm-1;

UY (98% H2S0j^) 245 (£49,300), 276 (£4 9,0 00), 341 (£2690),

and 360 (61350). Anal. Calcd. for C, 8 5.7 ; H, 7-15• Found:

C, 85-9; H, 7.25.

1.10-Cvclooctadecadione 31c Over a period of three hours, 44.6 g (0.12 mol) of sebacyl dichloride, dissolved in 300 ml of anhydrous benzene, was added to a refluxing solution containing

four litres of benzene and 250 ml of triethylamine (dried over potassium hydroxide). The mixture was stirred at room temperature for an additional three- hours. After standing overnight, the mixture was filtered and the benzene distilled under reduced pres sure. The residue was cooled to 0° and 25 g of potas sium hydroxide in 100 ml of methanol was added slowly. The solution was heated to reflux temperature for one hour, at which time 100 ml of water was added. After

the mixture was refluxed for two hours, the methanol was removed under diminished pressure. The aqueous mixture was extracted with ether, the ether layer dried over anhydrous magnesium sulfate, and filtered. The residue was crystallized from 2-propanol to give 6 .7 g (40$)

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. of product} m.p. 93-95° (lit.-^ 9 5-9 6 0).

6.6*;8.S'-Bishexamethvlenedibenzotro-pone 30c In the presence of 100 ml of a saturated solution

of sodium hydroxide in methanol was placed 1 .0 5 g (0 .0 0 8 mol) of phthalaldehyde, 1 .2 g (0.004- mol) of 1 ,1 0-cyclooctadecadione (31c). and 200 ml of ethanol.

The mixture was heated at reflux temperature for li hours, and then allowed to stand at room temperature overnight. The solution was filtered, and the solid

crystallized from tetrahydrofuran to give 1 .9 g (55f°) of white crystals; m.p. 264— 265°; IR(Nujol) 1595 (C=0)

and 1627 (C=C) cm-1; UV (98$ HgSO^) 244- (645,500), 277 (£44,800), 342 (6 2170), and 360 (61620) nm. Anal. Calcd. for C, 85.75; H,7*6.

Found: C, 85.55; H, 7 .8 5.

Dodecanedioyl dichloride Thirty grams of 1,12-dodecanedioic acid (0.13 mol) and sixty-two grams (0.53 mol) of thionyl chloride were heated at reflux for one hour. The excess

thionyl chloride was removed under reduced pressure, and the residue distilled to give 28 g (80$) of the dichloride; b.p. 151-154°/0.2 mm (lit.^ 162/1.6 mm).

1,12-Cyclodocosadione 31d Over a period of three hours, 28 g (0.1 mol) of

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dodecanedioyl dochloride in 250 ml of anhydrous henzene was added to a refluxing solution containing 3*5 litres of henzene and 250 ml of triethylamine (dried over potassium hydroxide). The solution was then allowed to stir at room temperature for three hours, at which time the mixture was filtered, and the henzene removed under reduced pressure. The residue was cooled to 0° and 25 g of potassium hydroxide in 100 ml of methanol was added slowly. After the mixture was refluxed for one hour, 100 ml of water was added and the solution was allowed to reflux for another hour. The methanol was removed under diminished pressure, and the aqueous solution extracted with ether. The ether extract was dried over anhydrous magnesium sulfate, filtered, and evaporated hy reduced pressure. The residue was crystallized from a water/2-propanol mixture to give 7*0 g (20$) of the

diketone; m.p. 52-53° (lit.-^ 53-5^°)•

6.6* ;8.81-Bisoctamethylenedibenzotropone 30d A solution containing 1.05 g (0.008 mol) of

phthalaldehyde, 1.3^ g (0.00k mol) of 1,12-cyclodocosadione (31d). 200 ml of ethanol, and 100 ml of saturated sodium hydroxide in methanol was heated to reflux temperature for 1§ hours. The mixture was allowed to cool and a solid appeared, which was crystallized from carhon tetrachloride to give 0.86 g

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(41%) of product containing a lsl mole ratio of carton

tetrachloride in the crystal lattice; m.p. 208-209°; MR(CD3CN) 6 1.0-2.9 (m, 32H, (CH2)l6), 7.4 (s, 4H, H&), 7.5-7.7 (m, 8H, ArH); IR(Nujol) 1605 (C=0), and 1626 (C=C) cm-1; UV (98% HgSO^) 241 (€73.800), 277 (€71,000),

340 (6 4010), and 356 (£229) nm. Anal. Calcd, for C^gH^Og'CCl^: C, 70.4; H, 6.65*

Founds C, 70.3; H, 6.75*

Preparation of Benzohomotropones

Trimethvloxosulfonium iodide A solution containing 48 g (0.68 mol) of dimethyl

sulfoxide and 205 g (1.45 mol) of methyl iodide was refluxed under nitrogen for three days. The solid was filtered, washed with chloroform, and crystallized from

water to give 52 g (37%) of colorless prisms of the

iodide.

40 Trimethvloxosulfonium chloride Twenty-five grams (0.12 mol) of trimethyloxo-

sulfonium iodide was dissolved in 250 ml of water and heated to 50?. Chlorine gas was bubbled into the well- stirred solution until no more iodine percipitated. The mixture was cooled, the aqueous portion decanted

from the iodine, and the iodine washed with water. The combined aqueous solutions were washed with ether until

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colorless. The water was then removed under reduced pressure. The residue was crystallized from methanol/ water to give 9*1 g (63fo) of colorless needles. The product was dried under vacuum at 85° for five hours.

Dimethvloxosulfonium methvlide (method of E.J. Corey^0) Six grams (0.125 mol) of a 5C$ mineral oil dispersion of sodium hydride was washed with three 20 ml portions of 30-600 petroleum ether. In the same flask was placed 26 g (0 .1 2 mol) of trimethyloxosulfonium

chloride and 250 ml of dry tetrahydrofuran (distilled from lithium aluminum hydride). The system was placed under nitrogen and heated to reflux, while stirring. The rapid evolution of hydrogen ceased after five min utes. After three hours, the mixture was cooled and filtered rapidly by vacuum using dried Celite filter-aid. The filtrate was immediately placed in a storage flask and sealed with rubber stopples and placed under nitrogen. A hypodermic syringe was used to withdraw the sample. The ylide can be stored for several weeks without appreciable decomposition.

la.3-Nonamethvlenebenzohomotropone 36 (method of Sugimura ^°) A solution of dimethylsulfonium methylide (0.010 mol) in tetrahydrofuran was added dropwise to 1 .0 g

(O.OO36 mol) of 6,8-nonamethylenebenzotroppne (25d) in

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5 ml of dry tetrahydrofuran at 0°. The system was under nitrogen and stirred vigorously. After the addition of the ylide the mixture was allowed to warm to room temperature and stirred overnight. The tetra hydrofuran was removed under reduced pressure and water was added. The mixture was extracted with ether, and

the ether layer dried over anhydrous magnesium sulfate, and filtered. The ether was then removed under reduced pressure. The residue was crystallized from methanol to yield 0.5 g (50$) of white crystals; m.p. 131-132°; NMR (CDCl^) 6 1.0-2.6 (m, 21H, ( C H ^ , CH2 , CH), 6.6 (d, 1H, Ha), ?.1-7.4 (m, 4H, ArH); IR(Nujol) 1640 (C=0) and 1580

(C=C) cm-1. Anal. Calcd. for C21H 260: C, 85*7; H, 8.85. Found:

C, 85-75; H, 8.9 .

Attempted preparation of la.3-dodecamethvlenebenzohomo- tropone (method of Sugimura ^°) A solution of dimethyloxosulfonium methylide (0.010 mol) in tetrahydrofuran was added dropwise to 1.0 g (0.004 mol) of 6,8-dodecamethylenehenzotropone (26f) in 10 ml of dry tetrahydrofuran at 0°. The system was under a nitrogen atmosphere. When the addition was completed the mixture was allowed to warm to room temp erature and stirred overnight. The tetrahydrofuran was evaporated and 50 ml of water was added. The mixture

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was extracted with ether, the non aqueous layer dried over anhydrous magnesium sulfate, filtered, and evap orated at reduced pressure. Analysis hy TIC indicated only starting material present. This was confirmed hy the melting point of a mixture of the product and the

starting material, (m.p. 64-66°)

Attempted synthesis of la,3-dodecamethvlenebenzohomo- tropone (method of Paquette^ ) Sodium hydride (0.1 g, 0.004 mol) dispersion was

washed with three 15 nil portions of pentane. To the sodium hydride was added 3 nil of dimethyl sulfoxide (dried hy distillation from calcium hydride) and 0.95 g (0.004 mol) of trimethyloxosulfonium iodide. After the cessation of hydrogen evolution, 1.3 g (0.004 mol) of

6,8-dodecamethylenebenzotropone (25f) in 3 ml of dimethyl sulfoxide and 1 ml of tetrahydrofuran was added dropwise to the cooled (0°) ylide. The mixture was poured into 75 ml of ether, washed with water, and dried over anhydrous magnesium sulfate. After filtration and evaporation under reduced pressure,

a solid appeared. This proved to he identical to the starting material by TLC analysis and the melting point of a mixture of the product and starting

material, (m.p. 64-66°)

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Attempted synthesis of 6.6* :8.8,-'bispolymethylene- dibenzohomotropones 30a and 30b Sodium hydride (1.03 mmol) was washed with pentane, and 1 ml of dimethylsulfoxide added, followed by .1 mmol of trimethyloxosulfonium iodide. To this cooled suspension (0°) was added 0.5 mmol of the bisditropone, 30a or 30b, in 1 ml of tetrahydrofuran and 0.5 ml of

dimethylsulfoxide over a period of 15 minutes. The mixture was allowed to warm to room temperature and stirred overnight. The mixture was poured into 50 ml of ether, washed with water, the ether layer dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure. The residue proved to be starting material by TLC analysis.

la.3-Nonamethylenebenzohomotropylium cation 37

Dissolving 0.5 g of 3 5 (0.002 mol) in perdeuterated sulfuric acid furnished a green solution which was analyzed at once by NMR spectroscopy since the sample decomposed very quickly at room temperature as indicated by the color change; NMR (DgSO^) 6 -0.35 (s, 1H, endo H), 0.^5-4.0 (m, 21H, ( C H ^ , exo H,

CH2, CH), 7.1-7.4 (m, 4H, ArH), 7 .^ (s, 1H, H&).

la.3a-Pentamethylenebenzodihomotropone 38 Sodium hydride (0.17 g, ^ mmol) dispersion was washed with three 15 ml portions of pentane. To the

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. sodium hydride was added O .83 g (3*75 mmol) of trimethyloxosulfonium iodide and 1 .9 ml of dimethylsulfoxide. The mixture was cooled to 0° and placed under nitrogen. Over a period of 15 minutes 0 .2 0 g (0 .9 mmol) of 2j>a

in 2 ml of tetrahydrofuran and 0 .3 ml of dimethyl

sulf oxide was added. The mixture was allowed to warm to room temperature and stir overnight. The mixture was poured into 50 ml of ether and washed with water. The ether layer was dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure to give 0 .1 5 g (68%) of white needles;

m.p. 135-1360; NMR(CDC13) 6 1.4-2.5 (m, 10H (CHg)^), 3.25 (d, to, CH2), 3 - (s, 2H, CH2), 4.0 (m, 2H, CH) 7.1-7.3 (m, to, ArH); IR(Nujol) 1180 (C-0) cm1).

Preparation of Tropolone Derivatives

Tropolone 2 (method of Stevens-^1 )

A solution containing 9 .0 g (0.05 mol) of 7,7- dichlorohicyclo[3.2.0]hept-2-en-6-one (22.), 13 g of potassium hydroxide, 150 ml of glacial acetic acid, and 150 ml of water was heated at reflux for 22 hours. The mixture was then cooled and 15 ml of a saturated aqueous copper (II) sulfate solution was added, followed hy 25 g of sodium carbonate. The mixture was extracted with methylene chloride and

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. the solvent then removed by distillation under reduced

pressure. The residue was dissolved in chloroform and then hydrogen sulfide gas was bubbled into the mixture. The mixture was filtered by suction using a Celite filter-aid. The filtrate was concentrated under dim inished pressure and the residue crystallized from hexane to give 1 .9 g (30#) of product; m.p. 47-49° (lit.49- 50°); NMR (CDC13) 6 9-51 (s, 1H, OH), 7*0-7.4 (m, 5H, C-H); IR(CCl^) 3100 (C-0) and 1615 (C=C) cm"1 .

4.5-Benzotronolone 40 (method of Stevens"’1) A mixture containing 10 g (0.047 mol) of 2,3- benzo-7 ,7 -dichlorobicyclo[3.2.0]]heptan-6-one (41), 7*2 g of potassium acetate, 100 ml of glacial acetic acid, and 100 ml of water was heated on a steam bath for two days. Upon cooling, crystals began to separate. The crystals were collected and recrystallized from ethanol to give 6 .6 g (81#) of product; m.p. 156-157° (lit. 49 158-159°i NMR (CDC13) 7.05-7.95 (complex multiplet), 9-5 (s, OH); IR(Nujol) 1635 (C=C) and 1618 (C=0) cm"1 .

2-Methoxv-4.6-benzotronolone 42 (method of J. Barltrop-^) Three grams of 4,5-benzotropolone (0.18 mol), 12 g

(0 .1 mol) of dimethylsulfate, and 75 ml of a 65# aqueous potassium hydroxide solution were stirred at room

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temperature for 15 hours. The mixture was filtered and then extracted with henzene. The henzene extracts were washed several times with water, dried over anhydrous magnesium sulfate, and filtered. Removal of the henzene under reduced pressure gave a residue which was crystal lized from cyclohexane to yield 1.^ g (kjfo) of k2j m.p.

87-88° (lit.50 89-90°); NMR (CH^CN) 6 3*9 (s, 3H, 0CH3), 6.8-7.4 (m,3H, C-H), 7.-4-7.6 (m, 4-H, ArH); IR(Nujol 1630

(C=C) and 987 (0-C) cm-1.

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A series of 6,8-polymethylenebenzotropones were prepared in order to study the effect of the polymethylene bridge on the aromaticity and the planarity of the tropylium ions. These compounds were prepared by the condensation of cyclic ketones and phthalaldehyde. We were able to confirm that the tropone ring system is planar only if n $ 7- Reduction of the benzotropones with lithium aluminum hydride afforded the corresponding alcohol, which was converted to the 6,8-polymethylene- benzotropylium perchlorate. This salt formed only if the tropone ring was planar. Also, the proton NMR spectra of these compounds indicates that the positive charge is delocalized over both the six and the seven membered

rings. The synthesis of the 6,6':8,8’-bispolymethylenedibenzotropones was accomplished by the condensation of two equivalents of phthalaldehyde with a cyclic diketone. Both IR and proton NMR analysis indicate that the tropone ring is planar. Treatment of the bisbenzotropones with lithium aluminum hydride afforded the corresponding dialcohol. This dialcohol was treated with perchloric acid to yield the 6,6':8,8'-polymethylenedibenzotropylium

perchlorate. This is an example of an ion with two

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. positive charges on the same molecule. The polymethylenebenzohomotropone formed readily when n = 9, hut would not form if n = 12 or for the bisbenzotropones. Evidently, steric hinderance inter feres with the cyclopropanation. Proton NMR indicates that the cyclopropyl ring is a disruptor of conjugation. Treatment of the polymethylenebenzohomotropone with deuterated sulfuric acid afforded the corresponding polymethylenebenzohomotroylium'ion. NMR analysis indicated that the positive charge was delocalized over only the homotropylium ion ring, and not over the six-membered ring. Finally, addition of the sulfur ylide to 6,8-pentamethylenebenzotropone seemed to result in both cyclopropanation and epoxidation.

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The author was born on December 19^2 in Detroit, Michigan. He received the degree of Bachleor of Science in Chemistry from Wayne State University in 1966. In 1968, he received the Master of Arts degree from Western Michigan University. The author has been a chemistry instructor at Portage Northern

High School for the last eight years. His interests include backpacking, astronomy, photography, and motorcycle touring. He is a member of the American Chemical Society. He has been married for six years.

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