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Bis-(p-3,5-dioxo-1,2,4-triazoline-4-ylphenyl)-methane and its reactions with diallyl compounds

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Bis-(p-3,5-dioxo-1,2,4-triazoline-4-ylphenyl)-methane and its reactions with diallyl compounds
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Ruch, Wayne Eugene, 1946-
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iii, 44 leaves : ill. ; 28cm.

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Subjects / Keywords:
Adducts ( jstor )
Copolymers ( jstor )
Hexanes ( jstor )
Magnetic spectroscopy ( jstor )
Molecular weight ( jstor )
Nuclear magnetic resonance ( jstor )
Polymers ( jstor )
Precipitates ( jstor )
Room temperature ( jstor )
Solvents ( jstor )
Chemistry thesis Ph. D
Diels-Alder reaction ( lcsh )
Dissertations, Academic -- Chemistry -- UF
Polymers and polymerization ( lcsh )
Triazoline ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (M. S.)--University of Florida.
Bibliography:
Bibliography: leaves 42-43.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Wayne Eugene Ruch.

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BIS- (p-3,5-DIOXO-i, 2,4-TRIAZOLINE-4-YLPHENYL)-METHANE AND
IT'S REACTIONS WITH DIALLYL CONPOUNDS








By



Wayne Eugene Ruch


A THESIS PRESENTED TO THE GRADUATE COUNCIL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE












UNIVERSITY OF FLORIDA


1975













TABLE OF CONTENTS



ABSTRACT .......................................... ......... iii

CHAPTER

I Introduction.................................... 1

II Results and Discussion ........................... 7

III Experimental ................ . .................... 26,

REFERENCES CITED......................................... 42

BIOGRAPHICAL SKETCH ...................................... 44








Abstract of Thesis Presented to the Graduate Council of the
University of Florida in Partial Fulfillment of the
Requirements for the Degree of Master of Science


BIS-(p-3,5-DIOXO-I,2,4-TRIAZOLINE-4-YLPHENYL)-MIETHANE AND

IT'S REACTIONS WITH DIALLYL COMPOUNDS By

Wayne Eugene Ruch

December, 1975

Chairman: Dr. G. B. Butler Major Department: Chemistry

This thesis presents a method of catalytic preparation of bis-(p-3,4-dioxo-l,2,4-triazoline-4-ylphenyl)-methane and the subsequent formation of a new class of polymers by the reaction of the bis compound and various diallyl compounds.

Evidence is presented to support the theory that the mechanism involved is a Diels-Alder-Ene mechanism.














Chairman


iii















CHAPTER I

INTRODUCTION



A. General Background

4-Phenyl-l,2,4-Triazoline-3,5-Dione,l, (PhTAD) was

first synthesized by Thiele1 in 1894 along with other members of the Triazoline-Dione family. These 4-substituted compounds were obtained by oxidizing the corresponding urazole, 2, with lead peroxide in cold, dilute sulfuric acid. Other oxidative methods used to date, have included treating the urazole with t-butyl hypochlorite in acetone,2 lead tetraacetate in methylene chloride,3 bromine,4 fuming nitric acid in cold methylene chloride,5 dinitrogen tetroxide gas in
6
methylene chloride, manganese dioxide, calcium hypochlorite or N-bromosuccinimide.





0
Q NN





This author has found the most effective method to be the use of catalytic amounts of fuming nitric acid.in methylene chloride at room temperature. Stirring inhibits









the reaction which also shows a short induction period. Purification of the PhTAD is accomplished by evaporation of the solvent and vacuum sublimation of the product.

Cookson, Gilani, and Stevens2 recognized the potential of PhTAD as a dienophile in Diels-Alder reactions. These researchers reported that low temperature solutions of PhTAD were stable in the absence of light and moisture, and would react with cyclopentadiene and butadiene to give the Diels-Alder adducts, 3, and 4, respectively.








00


These results lead to the use of PhTAD to prepare

Diels-Alder adducts of various steroids. 8,9 During these studies, it was noticed that PhTAD would react quickly even where maleic anhydride would not react at all. Sauer10 has done kinetic studies which show PhTAD to be one of the most powerful dienophiles existing. Evnin, Miller and Evanega report that a 1,4 cycloaddition product, 5, can be formed from cyclooctatetraene and PhTAD even though this reaction is not known to occur with other dienophiles. The compound PhTAD was used to trap Dewar benzene to give 6,12 reacted with cyclononatetraene to give 7,13 reacted with various cyclopentadiene derivatives. 1415 A 2:1 adduct of





















PhTAD with styrene can be formed by a double Diels-Alder reaction. 16 Reactions of PhTAD with vinyl compounds have been extensively studied.1720

Dienophiles can also undergo the Diels-ene reaction which is similar to the Diels-Alder reaction. This mechanism is shown in Scheme I. A Diels-ene type of product was found in the reaction of PhTAD and the alkene (4-phenylbutylidene)-cyclopropane. 21 Pirkle and Stickler22 performed SCHEME I













a series of kinetic studies and found PhTAD to be more than thirty thousand times as reactive as ethylazodicarboxylate with various monoolefins containing an a-hydrogen.









B. Research Objectives

The main objective of this study is to investigate the use of Triazoline-Diones in polymer formation.

Low molecular weight, alternating'copolyrers have been

reported by Turner, Guilbault, and Butler17 when vinyl ethers were reacted with Triazoline-Diones. Similar polymers were formed by the reaction of PhTAD with N-vinyl carbamates.19

Diels-Alder polymerization reactions are attractive,

for they offer a method of producing ladder-type high-temperature polymers. However, few Diels-Alder reactions have been able to produce high molecular weight polymers. 2vinylbutadiene undergoes a Diels-Alder self polymerization to form an insoluble compound,23 while,8, undergoes a DielsAlder self polymerization in refluxing xylene to give a low molecular weight oil. Diels-Alder polymerizations involving



0 -I (ft_100


9 9


the reaction of bidienes,lO, with bidieneophiles such as quinone,9, or N,N'-bis(maleimide),l, have been reported




,7
CH2U
III
C 970


- /


I I




5



to give polymers of low intrinsic viscosity and softening points below 2000 C.24 Other bidienes, including 2-vinylbutadiene,24 1,8-diphenyloctatetraene, 1,5-bis(9-anthryl)1,4-pentadiene-3-one, and anthralazine23 were used, but all gave only low molecular weight polymers. Reactions using bis(cyclopentadienyl) compounds as the bidiene were more successful,25 but high molecular weight, linear polymers were still not obtained.

Bis- (p-3,5-dioxo-l, 2,4-Triazoline-4-ylphenyl) -methane

o 0

1/ ~D-CHL

0 02

(BDTD), 12, has been used by Saville26 to crosslink natural rubber. The crosslinking was reported to have taken place by a Diels-ene reaction.

Reaction of BDTD, 12, with styrene was investigated by

Turner,27 who reported that a polymer was formed by a process which consisted of first a Diels-Alder reaction followed by a Diels-ene reaction on the product of the first reaction.
28
This reaction was later investigated in depth by Wagener, who confirmed the Diels-Alder-ene mechanism and determined that the reaction was giving a high molecular weight (& =

0.33 dl.g.) polymer. Wagener29 also reacted BDTD with divinyl esters of dicarboxylic acids. BDTD and diisopropyl adipate gave some low molecular weight and a large amount of insoluble solid. BDTD and divinyl adipate gave an insoluble gel in tetrahydrofuran.




6




The high reactivity of triazoline-diones,10 their 28
ability to form high molecular weight polymers, and the facility with which they undergo the Diels-ene reaction,22 suggest the possibility that useful, high molecular weight copolymers may be prepared by the reaction of BDTD with

various diallyl compounds.













CHAPTER II

RESULTS AND DISCUSSION



A. Formation of Diels-Ene Copolymers

Previous Results

Cookson, Gilani and Steves reported that a double

Diels-Alder product,13, was formed by the reaction of PhTAD and styrene. Wagener,30 investigating a reaction reported by Turner,27 showed that this product was actually a mixture of a double Diels-Alder adduct and a Diels-Alder-ene adduct, 14, with the latter being formed in twice the amount of the






~/q
05
0 5

\.IV






former. The reaction was repeated with 4-Methyl-l,2,4triazoline-dione,l5, which gave the same product ratio of 2:1 in favor of the Diels-Alder-ene adduct. he mechanism 20
suggested by Wagener, an elaboration of the mechanism of


Turner,27 is found in Scheme II.









SCHEME II


0k


1 A


The formation of a double addition product by reaction of PhTAD with styrene suggests the possibility of formation of a copolymer by reacting BDTD,12, with styrene. This reaction was performed by Turner,27 who reported the formation of a copolymer whose nuclear magnetic resonance spectrum gave evidence of a Diels-Alder-ene type of structure, 16. This reaction was studied in more detail by Wagener,28 who reported that reaction of concentrated solutions of BDTD in dimethyl formamide, when added to an equimolar amount of styrene, gave a high molecular weight copolymer. This









copolymer was found to consist of a mixture of Diels-Alderene repeat units, 16, and double Diels-Alder repeat units, 17.
- 0


C H_ +


C4L


17b
0


0/,



'7




Styrene was also copolymerized with 1,6-hexane-bis-l,2,4Triazoline-dione,18, which yielded a low molecular weight
0 0



0


(8









of 2300.20 The nuclear magnetic resonance spectrum for this polymer indicated that the Diels-Alder-ene unit was present in twice the amount of the double Diels-Alder unit.



B. Formation of New Copolymers

The BDTD used in this study was prepared by a modification of the method used by Saville.26

One mole of bis-(4-isocyanatophenyl)methane,19, was reacted with two moles of ethyl carbazate,20, to give the bis-semicarbazide,21. The bis-semicarbazide was cyclized by dissolving it in a 2M solution of potassium hydroxide, and then neutralizing the resulting solution with hydrochloric acid to give the bis-urazole,22. The bis-urazole
0 0) 0


N1 I I










00
-, C/i IUA1AI&/9HAJ% C


0 42-1/V( 2



was then oxidized to form the bis-Triazoline-dione,23, by either of two methods. During the early stages of these









studies, the urazole was oxidized by bubbling N204 gas through a stirred slurry of the urazole in methylene chloride at room temperature. As the oxidized product,23, was formed, it dissolved in the methylene chloride solvent to give a bright red solution which is characteristic of Triazolinediones. During the latter part of these studies, it was discovered that the reaction time could be shortened considerably if fuming nitric acid was substituted for the N204 gas, and if the reaction mixture was not stirred. Only catalytic amounts of the fuming nitric acid are necessary for oxidation to take place. Amounts used were typically on the order of five drops of fuming nitric acid for each gram of the urazole to be oxidized. Since the bis-Triazolinedione was decomposed slowly by the moisture in the air, while the urazole was unaffected, the compound was stored as the urazole and the required amount oxidized to Triazoline-dione immediately prior to use. The product formed by either method of oxidation was shown to be the same compound by infrared, nuclear magnetic resonance and elemental analysis.

The bis-Triazoline-dione is very soluble in polar solvents to give bright red solutions, but decomposes in two hours in dimethyl sulfoxide, one hour in dimethyl-formamide, and decomposes in one and one-half hours with formation of a tan precipitate in tetrahydrofuran. It is also decomposed in less than fifteen minutes by wet acetone. The bisTriazoline-dione was found to be stable for over forty-








eight hours when dissolved in a 50/50 mixture of reagent grade acetone and ethyl acetate, thus all reactions involving BDTD were carried out in this solvent mixture.

Since PhTAD undergoes the Diels-ene reaction readily with the allyl system,21'22 the possibility was suggested for the formation of copolymers by reacting BDTD, which also forms compounds by the Diels-ene pathway,28 with compounds that contain more than one allyl group. To investigate this possibility, BDTD was reacted with 1,6-heptadiene,24, diallyl ether, 25, triallylamine,26, diallylpropylamine,27, diallyldimethylsilane,28, diallylmethylphenylsilane,29, diallyldiphenylsilane,30, and 2,6-diallyl-3,5-dimethoxyphenol,31.


7


2-I



/ .../ c.'7


Al __ __


7 Z7 Cft3 3O �


L C H3 C 3


00


0
Cft~o c


K


/7
2z7


The heptadiene,24, and the ether,25, both reacted slowly, taking over twenty-four hours to decolorize an equimolar








concentration of BDTD. The two amines,26, and,27, react instantaneously with an equimolar concentration of BDTD in acetone/ethyl acetate to form a thick white, insoluble precipitate. The diallylphenol,31, took nineteen hours to react. The ether,25, the amines,26, and,27, and the phenol, 31, gave products in the form of white solids which were insoluble in dimethylformamide, dimethyl sulfoxide, dichloromethane, acetone, ether, benzene, hexane, and chloroform. These products could also be heated to 3000 C. with no apparent effects. The heptadiene,24, also gave an insoluble product that would not melt below 3000 C., but would soften at 2870 C. Infrared spectra of these compounds indicated that they were copolymers of BDTD with the diallyl compounds and not a homopolymer of BDTD, a portion of which could be recovered in each case. It appears that the BDTD unit is capable of conferring a high degree of thermal stability to the copolymers that it forms.

Since all of the BDTD copolymers were insoluble, model compounds were prepared to be used in nuclear magnetic resonance studies to help determine the structure of the copolymers. This was done for all of the diallyl compounds mentioned above, except for the diallylphenol and the triallylamine, by reacting them with two equivalents of PhTAD. The products of these reactions,32,33, and,34, were readily purified by crystallization from chloroform, and soluble in solvents such as acetone and dichloromethane. Mass spectra,













x

33 CH?311 N-317


infrared spectra, nuclear magnetic spectra, and elemental analysis indicated that the compounds,32,33, and,34, were 2:1 adducts formed by a Diels-ene reaction of PhTAD on each of the allyl groups. An adduct was not obtained in the reaction of PhTAD with 2,6-diallyl-3,5-dimethoxyphenol,31, because the PhTAD was decomposed by the presence of the hydroxyl group. This was confirmed by the reaction of PhTAD with 3,5dimethoxyphenol,35, which gave immediate decolorization of the PhTAD solution. BDTD however, shows no change when added






0
C-H30: 1 OCI/3
3S
35.


to a solution of three equivalents of 3,5-dimethoxyphenol dissolved in a 50/50 mixture of acetone and ethyl acetate, and allowed to sit for forty-eight hours.

Since BDTD should undergo the same Diels-ene reaction that PhTAD does, the repeat units in the copolymers should








have structures that are analagous to the corresponding model compounds.
o 0 2q c ?

CH 22

0 ""2 '7 ,V_c 3117 Q H �<~ 2 0 t, 00 1- 25 C 153




361




Cross-linking may be expected by reaction of the Triazoline-dione unit with the vinyl structure formed in the copolymer,36, by the Diels-ene reaction, since studies by Turner, Guilbault, and Butler,18 and by Wagener,20 show that both PhTAD and BDTD react readily with a series of vinyl compounds. This type of cross-linking probably does not occur in the copolymers, for the compound,37, can be allowed






0 0
37


to sit for forty-eight hours in a solution of PhTAD dissolved in methylene chloride with no change in the elemental analysis of the recovered adduct,37, or in the nuclear magnetic resonance spectrum.








The reactions of BDTD with the silicon compounds,28, 29, and,30, did not produce insoluble precipitates as did the other diallyl compounds. Instead, these compounds reacted to give an insoluble film which Covered the inside of the reaction vessel. All the films produced were insoluble in dimethyl sulfoxide, dimethylformamide, acetone, ethyl acetate, methylene chloride, chloroform, ether, and hexane. They were partially soluble in a solution made by dissolving chromic acid in concentrated sulfuric acid. The films did differ in their mechanical properties. The film produced by the reaction of BDTD,12, and diallyldimethylsilane,28, was opaque and could be lifted off the glass surface of the reaction vessel in the form of rubbery sheets, which were flexible but had a very low shear strength. This compound had a softening point of 2040 C. and turned a transparent, dark red color at 2700 C. This decomposition product was very hard and upon subsequent heating to 3000 C. showed no further change. The films formed by the reaction of BDTD with diallylmethylphenylsilane,29, and of BDTD with diallyldiphenylsilane,30, were both a transparent gold color. Both of these films were strong and inflexible. They also adhered strongly to the glass of the reaction vessel and could not be removed as sheets as in the case of the diallyldimethyl copolymer, but instead had to be chipped off. The hardness of these films was approximately that of ice of the same thickness. The thickness of the polymer coating








was measured as being between 0.5 mm and 1.0 mm for both compounds. The two copolymers do differ in their thermal properties. The product of BDTD and diallylmethylphenylsilane,29, softened at 2550 C. and then decomposed to the transparent red compound described earlier at 2700 C., while the product of BDTD and diallyldiphenylsilane,30, softened at 262 C. and decomposed at 2700 C. to the same transparent red compound.

The rates of reaction of the silicon compounds,28,29, and,30, with BDTD showed a progression. Diallyldimethylsilane,28, reacted the fastest, taking one hour to decolorize a solution containing one equivalent of BDTD. Diallylmethylphenylsilane gave the next fastest rate, taking three hours to decolorize one equivalent of BDTD, while diallyldiphenylsilane gave the slowest reaction, taking four hours to decolorize the BDTD solution. This progression of rates is probably due to the added steric hinderance of the phenyl group compared to the methyl group.

There is a soluble product left in the acetone/ethyl acetate solvent in each of the reactions of BDTD with the silicone compounds. This product can be recovered by dripping the acetone/ethyl acetate solution into a ten-fold excess of hexane. In each case, this process gives a dispersion in which the droplets adhere to any surface present in the flask and cover the surface with a yellow film. These films are soluble in polar solvents and can be crys-








tallized from chloroform to give bright yellow crystals. These crystals showed the same changes in their physical properties with increasing temperature as did the corresponding insoluble compounds. The soluble fractions had the same infrared spectra and elemental analysis as did the corresponding insoluble compounds, thus they can be characterized as being the low molecular weight fractions of the insoluble polymers. Nuclear magnetic resonance spectra were taken of these soluble compounds, and they, along with the infrared spectra and elemental analysis of the insoluble films, support the presence of repeat units formed by a 1:1 Diels-ene reaction between the triazoline-dione units on BDTD with the allyl groups of the silane compounds.

tH /


C fl








C. Reaction of PhTAD with Diallydialkylsilanes

PhTAD,1, was reacted with diallyldimethylsilane,28, diallylmethylphenylsilane,29, and with diallyldiphenylsilane,30. These reactions showed a progression of rates with the dimethyl compound,28, and the methylphenyl compound,29, decolorizing a solution of two equivalents of PhTAD in methylene chloride, in less than five minutes. The diphenyl compound,30, required two hours and fifteen minutes to decolorize the same PhTAD solution. This was to be expected after the results of the reactions of these same silicon compounds with BDTD. Once again the steric hinderance of the two phenyl groups slows the reaction rate.

The products of these reactions with PhTAD were recovered by dripping the reaction mixture into a ten-fold excess of hexane with stirring. This procedure resulted in the form of a precipitate obtained from each mixture. These precipitates were then filtered, dried and recrystallized from chloroform. The crystallization gave bright yellow, granular crystals in each case. The results of elemental analysis and nuclear magnetic resonance spectra, did not agree with the expected structure,38.


39








A sample of all three compounds was submitted for mass spectral analysis, and the resulting spectra indicated a cyclic structure,39, from the molecular weights and the splitting patterns. This cyclic structure agrees with the



/ C1/3 CH3









results of the elemental analysis and the nuclear magnetic resonance spectra.

Reaction of PhTAD with allyltrimethylsilane,40, gave

a product,41, whose elemental analysis indicated it to be a 1:1 adduct as was expected. However, the nuclear magnetic resonance spectra of this compound shows the unambiguous pattern of an allyl group that is no longer attached to the silicon atom. The structure,41, was assigned to this C113

cI i CO13








compound. This structure is supported by the splitting patterns found in the mass spectrum of this compound.









This compound is not cyclic, but the structure infers that there was either a cyclic transition state or a cyclic intermediate involved in its formation. A possible transition state is the six center transition state of the

.405


\ A I / H


c H3


. jI


Diels-ene reaction, except in this case an Si atom is abstracted instead of an H atom. This reaction is probably facilitated by the possible interaction of the non-bonding electrons of the nitrogen with the empty d-orbitals of the silicon. Because of these d-orbitals, the mechanism might not be concerted, but may rather involve an intermediate,42,





00
II -I "II '










in which loss of the Si from the carbonium ion would be preferred to loss of a proton.








Application of this second possibility to the reaction of PhTAD with the diallyldialkylsilane compounds, yields a tentative mechanism for the formation of the products observed. This mechanism is shown in Scheme III.


SCHEME III


.PA R1 C/3 C I3

C -


q3


tiq


I


0

r~>r


The second intermediate,45, does not break the carbonsilicon bond as would happen in the first intermediate,43,


4_'


1-15-








for the nitrogen introduced in the first step is in a position where the non-bonding electrons can help abstract a proton to form the double bond. At the same time the proton transforms the triazoline-dione unit into a good leaving group to regenerate the tetravalent silicon.

The cyclic product,39, could still be formed if the

intermediate product,44, should undergo a normal Diels-ene reaction between the allyl group of the silicon and PhTAD to give the intermediate product,46. This is shown in Scheme IV.


SCHEME IV















/47


q17









The nitrogen of the newly added triazoline-dione unit could attack the silicon in an Sn2 manner to replace the triazoline-dione unit already bonded to the silicon atom to give,47. The unstable intermediate,47, could then form the final cyclic product,39, by loss of a proton. Silicon is known to be a center of attack for nucleophilic substitution reaction,31 and the negative charge of the leaving triazolinedione unit could be somewhat stabilized by resonance with the oxygen of the adjacent carbonyl group,47a.


D. Reaction of PhTAD with Acetone

In purifying some of the previously mentioned PhTAD adducts formed in 50/50 acetone-ethyl acetate solvent, a very soluble low molecular weight contaminant was found, whose increase in yield was directly proportional to the decrease in rate of the main reaction. The same compound could be obtained in high yield by allowing solutions of PhTAD in both 50/50 acetone-ethyl acetate and in dried acetone to sit until decolorization of the solution had occurred. The product could not be obtained from PhTAD in ethyl acetate. The product was an adduct of PhTAD and acetone, which formed in a very slow reaction. This compound was recovered by dripping the decolorized solution into a ten-fold excess of hexane. This resulted in a yellow oil which was purified by dissolving in methylene chloride and allowing crystals to grow. These crystals were bright yellow color and had a melting range of 1260 - 1270 C. The









nuclear magnetic resonance spectra of this compound,48, gave two sharp singlets at T = 7.9 and T = 5.6, and a multiplet in the aromatic region at T'= 2.5. These peaks had proton ratios of 3:3:5 respectively. Mass spectral splitting patterns, infrared spectra, and elemental analysis agree with the structure assigned,48. A mechanism can be written for this reaction of PhTAD with the enol form of the acetone molecule,49, which has the six center transition state common to the Diels-ene reaction.


9-z. CC - CH
.,1. 7$o ,,
7zcHL-C--I3






C/I3 C C//



The slow rate of the reaction is due to the low concentration of the enol form. This reaction suggests the possibility of polymer formation between BDTD and the correct diketones.

Cookson, Gilani and Stevens16 reported formation of this compound, l-acetonyl-4-phenyl-l,2,4-triazoline-3,5dione, m.p. 134 - 1360, in a similar manner; however, these authors did not suggest a mechanism for its formation.














CHAPTER III

EXPERIMENTAL



A. General Information

Nuclear magnetic spectra were taken on a Varian A-60 spectrometer and infrared spectra were taken on a Beckman IR-8 spectrophotometer. Mass spectra were taken on a Model MS-30 mass spectrometer.

Melting points were taken on a Fisher-Johns melting point apparatus and are reported in degrees centigrade uncorrected.

Elemental analysis were completed by Atlantic Microlab Inc., of Atlanta, Georgia.

All reagents used were obtained commercially and used as received except as noted. All solvents were commercial grade and used as received.



B. Synthesis of 4-Phenyl-l,2,4-Triazoline-3,5-Dione

Ethyl Carbazate3

Diethyl carbonate (1.80 mol., 200.0 g.) and 99% hydrazine hydrate (1.80 mol., 88.0 g.) were mixed together with continuous stirring for thirty minutes. This resulted in an exothermic reaction in which the two phases initially








present combined to form one phase. The product of this reaction was distilled twice at 950 C. and 12 mm. This gave a yield of 130 g. (74%) of a white solid, mp 45-460 (Lit.4
0
44-45.50).


1-Ethoxycarbonyl-4-phenylsemicarbizide32

Ethyl carbazate (0.62 mol., 60.0 g.) was dissolved in 200 ml benzene and cooled to 100 C. in a three-neck, 500 ml, round bottom flask fitted with an addition funnel, a mechanical stirrer, and a reflux condenser with a drying tube. Phenyl isocyanate (0.62 mol., 57.3 g.) was added dropwise through the addition funnel with stirring. This resulted in the formation of a white precipitate. After the addition was completed, the cold bath was removed and the mixture was refluxed for one half hour, during which time the white precipitate dissolved. When the solution was cooled to room temperature, the white precipitate reformed. This precipitate was filtered and washed twice with 75 ml portions of cold benzene. The yield was 108.6 g. (89.9%) of a white solid with a melting point of 1530 C (Lit. 32 1540).


4-Phenyl Urazole

l-Ethoxycarbonyl-4-phenylsemicarbazide (0.55 mol.,

124.0 g.) was dissolved in 300 ml of hot 4M potassium hydroxide with stirring. The resulting light yellow solution was filtered and cooled. The solution was cooled in an ice-bath









and acidified with 6M hydrochloric acid to give a large amount of white precipitate. The precipitate was collected by filtration and washed with enough cold water to remove any traces of acid. The washed precipitate was dried overnight in a vacuum oven yielding 71 g. (80.4%) of a white solid, mp 205-2070 C (Lit.32 206-207� C).


4-Phenyl-l,2,4-Triazoline-3,5-Dione

4-Phenyl urazole (3.43 x 10-2 mol., 6.0 g.) was placed in a 500 ml erlenmeyer flask with 100 ml dichloromethane. This mixture was allowed to sit unstirred at room temperature while 4 drops of fuming nitric acid was added. There was a short induction period, after which the white urazole turned red and dissolved in the dichloromethane to give a red solution. The dichloromethane solution was filtered and evaporated by blowing a stream of compressed air over the surface of the solution. This resulted in a bright red crystalline substance which sublimed at 800 C and 1.0 mm. This material was used immediately upon preparation. Yield

5.6 g. (95.5%).


C. Synthesis of Bis-(p-3,5-dioxo-l,2,4-triazoline-4ylphenyl)-methane26

Bis-(4-isocyanatophenyl) methane was purified by vacuum distillation to give a clear colorless liquid which solidified on standing to white needle crystals. The









isocyanate (61.7 g., .247 mol.) was dissolved in 300 ml benzene. The resulting solution was added dropwise to a solution of ethyl carbazate (51.4 g., .494 mol.) dissolved in 200 ml benzene and cooled sufficiently to keep the reaction temperature between 50 and 100 C. After the addition was completed, the solution was allowed to warm to room temperature. This resulted in a large amount of white precipitate which was filtered out and washed twice with cold 100 ml portions of benzene. The white precipitate was placed in a vacuum oven to dry overnight. This gave a white powder, mp 239-242� C (Lit.26 240-244� C). Yield 101 g. (91.2%).

The bis-semicarbazide formed above (.22 mol., 101 g.)

was dissolved in 500 ml 4M potassium hydroxide with stirring and heating to give a yellow-green solution. The solution was cooled to room temperature and acidified with 6M hydrochloric acid. This gave a large amount of white precipitate which was filtered out of the solution and washed with cold water. The washed precipitate was left in a vacuum oven to dry overnight. This gave a 94 g. (92.2%) yield of the bisurazole with mp 3180 (Lit. 26 3200).

The bis-urazole (4 g., .011 mol) was placed in a 50 ml erlenmeyer with 25 ml dichloromethane. This mixture was allowed to sit unstirred at room temperature while 4 drops of fuming nitric acid were added. This resulted in a reaction which formed a red solution. The dichloromethane was evaporated by blowing a stream of compressed air over









the surface of the liquid. This gave 5.2 g. (87%) of the bright red bis-triazoline-dione which decomposed at 3260 C (Lit. 26 3200).

Anal. Calc. C17H10N604 ; C, 56.36; H, 2.98; N, 23.20

Found: C, 56.28; H, 3.01; N, 23.33


D. Synthesis of New Copolymers

Reaction of BDTD with 1,6-heptadiene

BDTD (1.00 g., 2.77 x 10- mol.) was dissolved in 30 ml. 50/50 ethyl acetate/acetone cosolvent at room temperature. To the bright red solution which formed, 1.6-heptadiene (.266 g., 2.77 x 10-3 mol.) was added dropwise with stirring. There was no immediate color change observed. After two hours the solution had become orange in color, and was observed to be cloudy. 24 hours after the addition, there was a yellow layer of solid material covering the bottom of the reaction vessel. This solid was isolated, washed with dichloromethane, and dried. After drying, the solid was observed to be brittle, and could be easily crushed to a yellow powder. This solid would not melt below 3000 C, but would soften at 2870 C. Infrared absorbances were observed (KBr) 3500 (m,b), 3300 (m), 2980 (w), 1800 (m), 1730 (s,b), 1670 (w), 1600 (w), 1500 (m), 1430 (m), 1200 (w), 1000 (w), 970 (m), 760 (w) cm1.

Anal. Calcd. for 1:1 copolymer C24H21N604 : C, 63.03; H, 4.59; N, 18. 37.

Found: C, 63.92; H, 4.48; N, 18.28.









Reaction of BDTD with Diallyl Ether

BDTD (1.00 ., 2.77 x 10-3 mol.) was dissolved in 20 ml 50/50 ethyl acetate/acetone cosolvent at room temperature. Diallyl ether (.271 g., 2.77 x 10-3 mol.) dissolved in 10 ml 50/50 ethyl acetate/acetone, was added dropwise with stirring. After 43 hours, the reaction mixture was still a pale pink in color and had a heavy suspension of pink particles. These particles were so fine that they would pass through a medium glass frit and completely clog a fine glass frit. It was discovered that upon addition of 25 ml hexane, the particles would clump together and could be filtered with a coarse glass frit. After washing with acetone and drying, a white powder (1.12 g., 88% yield) was obtained. This compound was heated to 3000 C. with no visible change. Infrared absorbances were found at (KBr) 3500 (m), 3300 (m), 2990 (w), 1800

(m), 1730 (s), 1640 (s), 1610 (s), 1600 (m), 1510 (m), 1440

(m), 1290 (s), 1200 (w), 1000 (w), 760 (w) cm-I.

Anal. Calcd. for 1:1 copolymer C23H19N605 C, 60.15; H, 4.14; N, 18.29.

Found: C, 60.23; H, 4.08; N, 18.36.


Reaction of BDTD with Diallylpropylamine

BDTD (1.00 g., 2.77 x 10-3 mol.) was dissolved in 20 ml 50/50 ethyl acetate/acetone. To this, a solution of diallylpropylamine (.377 g., 2.77 x 10-3 mol.) in 10 ml 50/50 ethyl acetate/acetone, was added dropwise with stirring. The reaction was instantaneous, resulting in decolorization of








the red BDTD solution and formation of a heavy, white precipitate. Yield of white powder after washing and drying was 1.31. g. (92.4%). This powder could be heated to 3000 C. with no visual change. Infrared absorbances were found at (KBr) 3500 (m), 3350 (m), 3000 (w), 1810 (m), 1740 (s), 1600 (w), 1500 (m), 1440 (m), 1300 (s), 1220 (s), 1200 (m), 1160 (m), 1050 (m), 1000 (w), 770 (w).

Anal. Calcd. for 1:1 copolymer C26H26N704 C, 62.42: H, 5.20: N, 19.59: 0, 12.79.

Found: C, 62.54; H, 5.28; N, 19.73.


Reaction of BDTD with Triallylamine

BDTD (1.5 g., 4.66 x 10-3 mol.) was dissolved in 30 ml

50/50 ethyl acetate/acetone. To this was added triallylamine (.377 g., 2.77 x 10-3 mol.) dissolved in 10 ml 50/50 ethyl acetate/acetone. The amine solution was added dropwise with stirring at room temperature. This resulted in instantaneous decolorization of the red BDTD solution and immediate formation of a white clump of solid material. This clump had the consistency of dried mud while still under the solvent and could be crushed easily with a stirring rod to a white powder. After washing with acetone and drying, the yield was 1.83 g., 95.7%. This material would darken at 2240 C, but still had not softened at 3000 C. Infrared absorbances were found at (KBr) 3500 (m), 3250 (m), 3000

(w), 1800 (m), 1730 (s), 1600 (w), 1500 (m), 1420 (m),








1360 (s), 1280 (s), 1200 (w), 1100 (m), 1020 (w), 750 (w).

Anal. Calcd. for 1:1 copolymer C36H33N1006: C, 61.64; H, 4.71; N, 19.96; 0, 13.69.

Found: C, 61.70; H, 4.56; N, 20.13.


Reaction of BDTD with 2,6-diallyl-3,5-dimethoxyphenol

BDTD (1.00 g., 2.77 x 10-3 mol.) was dissolved in 20 ml 50/50 ethyl acetate/acetone. 2,6-diallyl-3,5-dimethoxyphenol (.651 g., 2.77 x 10-3 mol.) was dissolved in 10 ml 50/50 ethyl acetate/acetone, and this was added dropwise to the BDTD solution with stirring at room temperature. After a reaction time of nineteen hours, the solution had changed from a bright red color to a pale yellow color with a waxy white substance covering the bottom of the flask. This material was isolated by decanting the liquid of, adding fresh acetone and grinding the material under acetone. This procedure was repeated twice with 15 ml portions of acetone and one 15 ml portion of dichloromethane. This treatment turned the white wax to a white powder, which was allowed to air dry. Yield 1.06 g. (64.2%). This powder was heated to 3000 C. with no visible change. Infrared absorbances were found at (KBr) 3600 (w), 3300 (m), 2980 (w), 2850 (s), 1950 (m), 1810 (m), 1730 (s), 1640 (s), 1620 (s), 1590 (m), 1500 (m), 1430 (m), 1410 (m), 1200 (w), 1000 (w), 840 (m), 760 (w) cm1.

Anal. Calcd. for 1:1 copolymer: C31H27N607: C, 62.54;








H, 4.53; N, 14.11; 0, 18.81.

Found: C, 62.35; H, 4.59; N, 14.34.


Reaction of BDTD with Diallyldimethylsilane

Diallyldimethylsilane (.388 g., 2.77 x 10-3 mol.) was weighed into a flask containing 10 ml 50/50 ethyl acetate/ acetone. To this solution, another solution consisting of BDTD (1.00 g., 2.77 x 10-3 mol.) dissolved in 20 ml 50/50 ethyl acetate/acetone was added dropwise, at room temperature with stirring. Midway through the addition, the reaction mixture was red in color, but had started to turn opaque. One hour after the addition had been completed, the mixture had turned a light golden yellow and a film was observed covering the entire inside surface of the reaction vessel up to the solvent level. The solvent was decanted off and the film allowed to dry. The film was opaque and did not adhere to the reaction vessel, instead it could be stripped off in flexible sheets. These sheets were insoluble in all solvents tried and only partially soluble in C 03/H2So4. The film was washed in acetone and dried. Yield 1.15 g (83.0%). Softened at 2040 C., turned dark red at 2700 and showed no further change at 3000 C. Infrared absorbances were found at (KBr) 3500 (m), 3330 (m), 3000 (w), 1800 (m), 1750 (m) 1670 (w), 1500 (m), 1410 (m), 1260 (s),
-I
1200 (m), 1000 (w), 950 (m), 840 (s), 760 (w) cm

Anal. Calcd. for 1:1 copolymer C25H25N604Si: C,









59.89; H, 4.99; N, 16.75; 0, 12.76; Si, 5.60.

Found: C, 59.84; H, 5.01; N, 16.40.


Reaction of BDTD with DiallylmethyIphenylsilane

Diallylmethylphenylsilane (.560 g., 2.77 x 10-3 m) was weighed into a flask containing 10 ml. 50/50 ethyl acetate/acetone. To this solution another solution containing BDTD (1.00 g., 2.77 x 10-3.m) dissolved in 20 ml 50/50 ethyl acetate/acetone was added dropwise with stirring. One hour after addition the mixture was still red, but a film could be seen growing on the side of the reaction vessel. After six hours the solvent was poured off and the film allowed to air dry. After drying this film was found to adhere strongly to the glass vessel, but could be chipped off. Yield 1.35 g. (86.6%). Infrared absorbances were found at (KBr) 3500 (m), 3300 (m), 3000 (w), 1820 (m), 1750

(m), 1670 (m), 1630 (m), 1490 (m), 1430 (m), 1260 (s), 1200

(w), 1130 (s), 1000 (w) 970 (m), 830 (s), 760 (w) cm-I.

Anal. Calcd. for 1:1 copolymer C29H27N604Si: C, 63.17; H, 4.90; N, 15.20; 0, 11.6; Si, 5.09.

Found: C, 63.22; H, 4.87; N, 15.37.


Reaction of BDTD with Diallyldiphenylsilane

Diallyldiphenylsilane (.731 g., 2.77 x 10 mol.) was weighed into a flask containing 10 ml 50/50 ethyl acetate/ acetone. To this solution, another solution consisting of BDTD (1.00 g., 2.77 x 10-3 mol.) dissolved in 20 ml 50/50








ethyl acetate/acetone was added dropwise with stirring at room temperature. A film was noticed on the sides of the flask but its growth was much slower than with the other two diallylsilanes. After six hours the solvent was poured off and the film allowed to air dry. This film adhered strongly to the sides and bottom of the flask. Yield 1.47 g (84.9%). M.P.: Softens 2620 C., decomposes 2700C. Infrared absorbances were found at (KBr) 3500 (m), 3300 (m), 2980

(w), 1810 (m), 1730 (s), 1600 (m), 1630 (s), 1510 (m), 1430

(n), 1220 (m), 1125 (s), 1000 (w), 970 (m), 750 (w).

Anal. Calcd. for 1:1 copolymer C34H29N604Si: C, 66.56; H, 4.75; N, 13.69; 0, 10.4; Si, 4.58.

Found: C, 66.43; H, 4.70; N, 13.79.


E. Formation of PhTAD Adducts

Reaction of PhTAD with Acetone

4-Phenyl-l,2,4-triazoline-3,5-Dione (.500g., 2.86 x

10-3 mole) was dissolved in 25 ml of acetone (reagent grade) which had been dried overnight over molecular sieves. The resulting bright red solution was allowed to react for 24 hours at room temperature. At the end of this period the now pale yellow solution was dripped into a 10-fold excess of hexane with stirring to give a golden oil which sank to the bottom of the hexane. The hexane was decanted and the oil purified by dissolving in methylene chloride and allowing crystals to grow. These were recrystallized from methylene chloride to give bright yellow, flat diamond shaped








crystals with a melting range of 1260 - 1270 C. Nuclear magnetic resonance signals were observed at (CDC13) 2.5 (m,5), 5.6 (s,2), 7.9 (s,3) T. Mass spectra data indicated the molecular weight to be 233 with major splitting pattern peaks at m/e 191, 190, 177, 119, 91, 77, 57, 43.

Anal. Calcd. for 1:1 adduct C11H N303: C, 56.67; H,

4.71; N, 18.02; 0, 20.59.

Found: C, 56.70; H, 4.68; N, 18.11.


Reaction of PhTAD with Allyltrimethylsilane

PhTAD (1.50 g., 8.58 x 10-3 mole) was dissolved in 25 ml dichloromethane, to give a bright red solution. This was added dropwise to a solution of allyltrimethylsilane (.978 g.,

8.58 x 10-3 mole) in 10 ml dichloromethane with stirring. The red PhTAD solution decolorized immediately upon entering the silane solution. The resulting solution was dripped into 350 ml of hexane. Evaporation of the hexane gave a thick oil. This was purified by dissolving in chloroform and adding enough hexane to induce crystallization. Yield,

1.81 g. (73.1%). Nuclear Magnetic resonance signals were observed at (CDCI3) S 0.18 (s,6), 6 4.20 (d,2), 6 5.33 (m,2), 6 6.0 (m,l), 6 7.46 (m,5). Mass spectral data gives parent peak at 289 with major splitting pattern peaks at:. 274, 234, 217, 200, 189, 177, 120, 91, 77, 73, 41.

Anal. Calcd. for 1:1 adduct C14H19N302Si: C, 58.13; H, 6.57; N, 14.52; 0, 11.06; Si, 9.71.

Found: C, 58.62; H, 6.43; N, 14.30.









Reaction of PhTAD with Diallyldimethylsilane

PhTAD (1.695 g., 9.69 x 10-3 mole) was dissolved in 20 ml of 50/50 acetone/ethyl acetate to give a bright red solution. A solution of diallyldimethylsilane (.678 g.,

4.85 x 10-3 mole) in 10 ml of 50/50 acetone/ethyl acetate was added dropwise with stirring at room temperature. The reaction was slightly exothermic. After the addition was complete, the mixture was still bright red but showed some cloudiness. After allowing to sit at room temperature for 24 hours, the solution was added dropwise with stirring to 300 ml of hexane to give a viscous orange oil. The oil was crystallized by grinding in a mortar and pestle with fresh hexane and drying under vacuum. The resulting fine orange powder was recrystallized from chloroform. Yield .858 g. (64.8%). M.P. - Softens at 620 C., Decomposes with evolution of gas at 750 C. Nuclear magnetic resonance signals were observed at (d6-acetone) S 0.28 (m,6); 6 4.30 (m,2);

6 5.32 (m,l); 6 5.92 (m,l); 6 7.52 (m,5). Molecular weight from mass spectral data: 273. Splitting pattern peaks at; 230, 217, 200, 189, 177, 160, 153, 139, 132, 120, 119, 100, 91, 83, 77.

Anal. Calcd. for 1:1 adduct,39, C13H15N302Si: C, 57.13; H, 5.49; N, 15.37; 0, 11.70; Si, 10.28.

Found: C, 56.98; H, 6.01; N, 15.44.









Reaction of PhTAD with Diallylmethylphenylsilane

PhTAD (.558 g., 3.19 x 10-3 mole) was dissolved in 40 ml of dichloromethane and diallylmethylphenylsilane (.215 g., 1.06 x 10-3 mole) was weighed directly into the solution. After allowing to sit at room temperature for 24 hours, this was dripped into 400 ml hexane at room temperature with stirring, to give a white precipitate which agglomerated on stirring. This precipitate was filtered, washed with hexane and purified by redissolving in dichloromethane and adjusting the solubility be adding enough hexane to initiate crystallization. Yield .282 g. (79.4%). M.P. 94-960 C. Nuclear magnetic resonance signals were observed at (D6-acetone): 6 0.52 (m,3); 6 4.20 (m,2); 6 6.20 (m,l); 6 6.62 (m,l); 6 7.45 (m,10). Molecular weight from mass spectral data; 335. Splitting pattern peaks at; 322, 293 (very small), 217, 202, 200, 189, 177, 174, 160, 145, 132, 121, 120, 91, 77.

Anal. Calcd. for compound,39,: C18H17N302Si: C, 64.47; H, 5.07; N, 12.52; 0, 9.54; Si, 8.38.

Found: C, 64.73; H, 4.97; N, 13.03.


Reaction of PhTAD with Diallyldiphenylsilane

PhTAD (.500 g., 2.86 x 10-3 mole) was dissolved in

40 ml of dichloromethane and diallyldiphenylsilane (.377 g.,

1.43 x 10-3 mole) was weighed directly into the solution. After allowing to sit for 24 hours at room temperature,









this was dripped into 400 ml hexane at room temperature with stirring. This results in a fine white precipitate which clumps together on stirring. This precipitate was collected by filtration, washed and purified by redissolving in dichloromethane and adding hexane to induce crystallization. Yield .402 g. (70.9%). M.P. 102 - 103.80 C. Nuclear magnetic resonance signals were observed at (D6-acetone):

6 4.26 (m,2); 6 6.35 (m,l); 6 6.72 (m,l); 6 7.38 (m,15). Molecular weight from mass spectral data: 397. Splitting pattern peaks at; 355, 277, 236, 224, 217, 177, 120, 119, 105, 91, 77.
Anal. Calcd. for compound,39,: C23H19N302Si: C, 69.52; H, 4.78; N, 10.57; 0, 8.05; Si, 7.07.

Found: C, 69.98; H, 4.39; N, 10.93.


Reaction of PhTAD with Diallylether

PhTAD (1.882 g., 1.07 x 10-2 mole) was dissolved in 30 ml of 50/50 ethyl acetate/acetone to give a bright red solution. Diallylether (.351 g., 0.35 x 10-2 mole) was added and the reaction mixture allowed to sit for 24 hours at room temperature. At the end of this time, the mixture was still a bright red, but lighter in color than the original PhTAD solution. The mixture was dripped into 300 ml hexane to give a pinkish white powder which was electrostatic on drying. This was purified by recrystallization from acetone. Yield 1.38 g. (88.2%). M.P. Behavior: De-









composes at 93.40 C. with evolution of gas. Nuclear magnetic resonance signals were observed at (D6-acetone):

6 4.22 (m,2); 6 5.00 (m,l); 6 5.82 (m,l); 6 7.36 (m,5);

6 8.5 (very broad,l). Molecular weight from mass spectral data: 448. Splitting pattern peaks at: 271, 231, 215, 203, 190, 176, 146, 120, 119, 93, 77, 69, 43.

Anal. Calcd. for 2:1 adduct: C20H 20N605: C, 58.95; H, 4.46; N, 18.74; 0, 17.85.

Found: C, 59.22; H, 4.50; N, 18.94.














REFERENCES CITED


1. J. Thiele and 0. Stange, Ann., 283, 1 (1894).

2. R.C. Cookson, S.S.H. Gilani, and I.D.R. Stevens, Tetrahedron Lett., 615 (1962).

3. B.T. Gillis and J.D. Hagarty, J. Org. Chem., 32, 330 (1967).

4. J. Sauer and B. Schroder, Ber., 100, 678 (1967).

5. F. Yoneda, K. Suzuki, and Y. Nitta, J. Amer. Chem. Soc.,
88, 2328 (1967).

6. J.C. Stickler and W.H. Pirkle, J. Org. Chem., 31, 3444 (1966).

7. J.C. Stickler, Ph. D. Dissertation, University of Illinois, 1971, p. 4.

8. A.J. Solo, H.S. Sachdev, and S.S.H. Gilani, J. Org. Chem.,
30, 769 (1965).

9. S.S.H. Gilani and D.J. Triggle, J. Org. Chem., 31, 2397
(1966).

10. J. Sauer, Angew. Chem., (1E) 6, 26 (1967). 11. A.B. Evnin, R.D. Miller, G.R. Evanega, Tetrahedron Lett.,
5863 (1968).

12. D.M. Lemal and J.P. Lokensgard, J. Amer. Chem. Soc., 88,
5934 (1966).
13. A.G. Anastassion and R.P. Celluca, Tetrahedron Lett.,
911 (1970).

14. C.M. Anderson, J.B. Bremmer, T.W. McCay, and R.N. Warrener,
ibid, 1255 (1968).










15. R. Breslow, J. Hoffman, M. Jacob, Jr., J. Amer. Chem.
Soc., 94, 2110 (1972).

16. R.C. Cookson, S.S.H. Gilani and I.D.R. Stevens, J. Chem.
Soc., 1905 (1967).

17. G.B. Butler, L.J. Guilbault and S.R. Turner, Polym.
Lett., 9, 113 (1971).

18. S.R. Turner, L.J. Guilbault and G.B. Butler, J. Org.
Chem., 36, 2838 (1971).

19. L.J. Guilbault, S.R. Turner and G.B. Butler, Polym.
Lett., 10, 1 (1972).

20. K.B. Wagener, Ph. D. Dissertation, University of Florida,
p. 60.

21. D.J. Pasto and A.F.T. Chen, Tetrahedron Lett., 2995
(1972).

22. W.H. Pirkle and J.C. Stickler, Chem. Comm., 760 (1967). 23. J.K. Stille, Fortsche. Hochpolymer Forsch., 3, 48 (1961). 24. W.J. Bailey, J. Economy and M.E. Hermes, J. Org. Chem.,
27, 3295 (1962).

25. J.K. Stille and L. Plummer, J. Org. Chem., 26, 4026
(1961).

26. B. Saville, J. Amer. Chem. Soc., 90, 635 (1971). 27. S.R. Turner, Ph. D. Dissertation, University of Florida,
p. 60.

28. K.B. Wagener, Ph. D. Dissertation, University of Florida,
p. 53.

29. K.B. Wagener, ibid., p. 43. 30. K.B. Wagener, ibid., p. 49. 31. Earborn, C. Organosilicon Compounds, 1960, Academic
Press.












BIOGRAPHICAL SKETCH


Wayne Eugene Ruch was born in Pittsburgh, Pennsylvania on November 24, 1946. He graduated from Avonworth High School in June of 1964 and received his Bachelor of Science Degree from the Chemistry Department of Carnegie Institute of Technology in June of 1968. During his senior year of college, he was employed by the Gulf Oil Catalysis Research Group at Mellon Institute.

The author was accepted for graduate studies at the Chemistry Department of the University of Florida for the fall of 1968 but was drafted to serve his country the following March. He served two years with the K-9 Corps of the U.S. Army, one year of which was spent as a tunnel dog handler with the 63rd combat tracker platoon of the Americal Division, where he was awarded the Bronze Star and an Oak Leaf Cluster to the Bronze Star. At the end of his service he returned to his studies.

In March of 1974 the author entered the employ of the Semiconductor Division of Harris Corporation as a senior engineer in the Materials Department. At present he is the engineer in charge of hard surface mask production.









I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a master's thesis for the degree of Master of Science.



'George B. Butler
Professor of Chemistry



I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a master's thesis for the degree of Master of Science.



Paul Tarrant
Professor of Chemistry



I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a master's thesis for the degree of Master of Science.



Thieo E. Hogan Esch
Asst. Professor of Chemistry



This thesis was submitted to the Graduate Faculty of the Department of Chemistry in the College of Arts and Sciences and to the Graduate Council, and was accepted as partial fulfillment of the requirements for the degree of Master of Science.

December, 1975


Dean, Graduate School




Full Text

PAGE 1

BIS(p-3, 5-DIOXO-l, 2 , 4-TRIAZ0LINE-4-YLPHENYL) -METHANE AND IT'S REACTIONS WITH DIALLYL COMPOUNDS By Wayne Eugene Ruch A THESIS PRESENTED TO THE GRADUATE COUNCIL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 1975

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TABLE OF CONTENTS ABSTRACT 3 1:L CHAPTER I Introduction 1 II Results and Discussion...... 7 III Experimental 26 REFERENCES CITED 42 BIOGRAPHICAL SKETCH 44 IX

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Abstract of Thesis Presented to the Graduate Council of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Science BIS(p-3 , 5-DI0X0-1 , 2 , 4-TRIAZ0LINE-4-YLPHENYL) -METHANE AND IT'S REACTIONS WITH DIALLYL COMPOUNDS By Wayne Eugene Ruch December, 1975 Chairman: Dr. G. B. Butler Major Department: Chemistry This thesis presents a method of catalytic preparation of bis (p-3 , 4-dioxo-l , 2 , 4triazoline-4-ylphenyl) -methane and the subsequent formation of a new class of polymers by the reaction of the bis compound and various diallyl compounds . Evidence is presented to support the theory that the mechanism involved is a Diels -Alder-Ene mechanism. Chairman m

PAGE 4

CHAPTER I INTRODUCTION A. General Background 4-Phenyl1 , 2 , 4-Triazoline-3 , 5-Dione , 1_, (PhTAD) was first synthesized by Thiele^ in 1894 along with other members of the Triazoline-Dione family. These 4-substituted compounds were obtained by oxidizing the corresponding urazole, 2, with lead peroxide in cold, dilute sulfuric acid. Other oxidative methods used to date, have included treating the 2 urazole with t-butyl hypochlorite in acetone, lead tetra3 A acetate in methylene chloride, bromine, fuming nitric acid in cold methylene chloride, dinitrogen tetroxide gas in methylene chloride, manganese dioxide, calcium hypochlorite or N-bromosuccinimide . ^ This author has found the most effective method to be the use of catalytic amounts of fuming nitric acid in methylene chloride at room temperature. Stirring inhibits 1

PAGE 5

2 the reaction which also shows a short induction period. Purification of the PhTAD is accomplished by evaporation of the solvent and vacuum sublimation of the product. 2 Cookson, Gilani, and Stevens recognized the potential of PhTAD as a dienophile in Diels-Alder reactions. These researchers reported that low temperature solutions of PhTAD were stable in the absence of light and moisture, and would react with cyclopentadiene and butadiene to give the Diels-Alder adducts, _3, and 4, respectively. These results lead to the use of PhTAD to prepare 8 9 Diels-Alder adducts of various steroids. Â’ During these studies, it was noticed that PhTAD would react quickly even where maleic anhydride would not react at all. Sauer^ has done kinetic studies which show PhTAD to be one of the most powerful dienophiles existing. Evnin, Miller and Evanega^ report that a 1,4 cycloaddition product, 5, can be formed from cyclooctatetraene and PhTAD even though this reaction is not known to occur with other dienophiles. The 12 compound PhTAD was used to trap Dewar benzene to give 6, 13 reacted with cyclononatetraene to give 7, reacted with various cyclopentadiene derivatives . ^ A 2:1 adduct of

PAGE 6

3 PhTAD with styrene can be formed by a double Diels -Alder reaction. Reactions of PhTAD with vinyl compounds have been extensively studied. ^ ^ . Dienophiles can also undergo the Diels -ene reaction which is similar to the Diels-Alder reaction. This mechanism is shown in Scheme I. A Diels -ene type of product was found in the reaction of PhTAD and the alkene (4-phenyl21 22 butylidene) -cyclopropane. Pirkle and Stickler performed SCHEME I a series of kinetic studies and found PhTAD to be more than thirty thousand times as reactive as ethylazodicarboxylate with various monoolefins containing an a-hydrogen.

PAGE 7

4 B. Research Objectives The main objective of this study is to investigate the use of Triazoline-Diones in polymer formation. Low molecular weight, alternating' copolymers have been reported by Turner, Guilbault, and Butler‘S when vinyl ethers were reacted with Triazoline-Diones. Similar polymers were 19 formed by the reaction of PhTAD with N-vinyl carbamates. Diels-Alder polymerization reactions are attractive, for they offer a method of producing ladder-type high-temperature polymers. However, few Diels-Alder reactions have been able to produce high molecular weight polymers. 2vinylbutadiene undergoes a Diels-Alder self polymerization 23 to form an insoluble compound, while, 8^, undergoes a DielsAlder self polymerization in refluxing xylene to give a low molecular weight oil. Diels-Alder polymerizations involving 8 the reaction of bidienes , 10^, with bidieneophiles such as quinone,9, or N,N' -bis (maleimide) , 11, have been reported 10

PAGE 8

5 to give polymers of low intrinsic viscosity and softening o *2 /j points below 200° C. Other bidienes, including 2-vinyl2 4 butadiene, ‘ + 1 , 8-diphenyloctatetraene , 1 , 5-bis (9-anthryl) 23 1 , 4-pentadiene-3-one , and anthralazine were used, but all gave only low molecular weight polymers. Reactions using bis (cyclopentadienyl) compounds as the bidiene were more 25 successful, but high molecular weight, linear polymers were still not obtained. Bis (p-3 , 5-dioxo-l , 2 , 4-Triazoline-4-ylphenyl) -methane (BDTD) , 12 , has been used by Saville^ to crosslink natural rubber. The crosslinking was reported to have taken place by a Diels-ene reaction. Reaction of BDTD, 12_, with styrene was investigated by 27 Turner, who reported that a polymer was formed by a process which consisted of first a Diels-Alder reaction followed by a Diels-ene reaction on the product of the first reaction. This reaction was later investigated in depth by Wagener, ° who confirmed the Diels -Alder-ene mechanism and determined that the reaction was giving a high molecular weight ( t\_ = 29 0.33 dl.g.) polymer. Wagener also reacted BDTD with divinyl esters of dicarboxylic acids. BDTD and diisopropyl adipate gave some low molecular weight and a large amount of insoluble solid. BDTD and divinyl adipate gave an insoluble gel in tetrahydrofuran.

PAGE 9

6 The high reactivity of triazoline-diones , their 2 8 ability to form high molecular weight polymers, c and the 22 facility with which they undergo the Diels-ene reaction, r suggest the possibility that useful, high molecular weight copolymers may be prepared by the reaction of BDTD with various diallyl compounds.

PAGE 10

CHAPTER II RESULTS AND DISCUSSION A. Formation of Diels -Ene Copolymers Previous Results Cookson, Gilani and Steves reported that a double Diels-Alder product, 13, was formed by the reaction of PhTAD 30 and styrene. Wagener, investigating a reaction reported 27 by Turner, showed that this product was actually a mixture of a double Diels-Alder adduct and a Diels -Alder-ene adduct, 14, with the latter being formed in twice the amount of the former. The reaction was repeated with 4-Methyl-l , 2 , 4triazoline-dione, 1_5 , which gave the same product ratio of 2:1 in favor of the Diels -Alder-ene adduct. The mechanism 20 suggested by Wagener, an elaboration of the mechanism of 27 Turner, is found in Scheme II. 7

PAGE 11

8 SCHEME II O lhe formation of a double addition product by reaction of PhTAD with styrene suggests the possibility of formation of a copolymer by reacting BDTD,12, with styrene. This reO *7 action was performed by Turner, x^ho reported the formation of a copolymer whose nuclear magnetic resonance spectrum gave evidence of a Diels-Alder-ene type of structure, 16. This reaction was studied in more detail by Wagener, 28 who reported that reaction of concentrated solutions of BDTD in dimethyl formamide, when added to an equimolar amount of styrene, gave a high molecular weight copolymer. This

PAGE 12

9 copolymer was found to consist of a mixture of Diels-Alderene repeat units, 16, and double Diels-Alder repeat units. Styrene was also copolymerized with 1, 6 -hexane -b is-1 , 2,4Triazoline-dione, 1_8, which yielded a low molecular weight O O A/' I. V. v* b 6 r 18

PAGE 13

10 20 of 2300. The nuclear magnetic resonance spectrum for this polymer indicated that the Diels-Alder-ene unit was present in twice the amount of the double Diels -Alder unit. B, Formation of New Copolymers The BDTD used in this study was prepared by a modifi2 6 cation of the method used by Saville. One mole of bis(4-isocyanatophenyl)methane, lk was reacted with two moles of ethyl carbazate , 20, to give the bis-semicarbazide , 21 . The bis-semicarbazide was cyclized by dissolving it in a 2M solution of potassium hydroxide, and then neutralizing the resulting solution with hydro The bis-urazole chloric acid to give the bis-urazole , 22 . k H. O ii ' u lH L MMHCo£t o o \EtQCN NCN jH H CH2 . xo 7~l V )^r KOH 2.) tfjd 5 was then oxidized to form the bis-Triazoline-dione, 23^, by either of two methods. During the early stages of these

PAGE 14

11 studies, the urazole was oxidized by bubbling gas through a stirred slurry of the urazole in methylene chloride at room temperature. As the oxidized product, Z3, was formed, it dissolved in the methylene chloride solvent to give a bright red solution which is characteristic of Triazolinediones. During the latter part of these studies, it was discovered that the reaction time could be shortened considerably if flaming nitric acid was substituted for the N 2 0^ gas, and if the reaction mixture was not stirred. Only catalytic amounts of the fuming nitric acid are necessary for oxidation to take place. Amounts used were typically on the order of five drops of fuming nitric acid for each gram of the urazole to be oxidized. Since the bis-Triazolinedione was decomposed slowly by the moisture in the air, while the urazole was unaffected, the compound was stored as the urazole and the required amount oxidized to Triazolinedione immediately prior to use. The product formed by either method of oxidation was shown to be the same compound by infrared, nuclear magnetic resonance and elemental analysis. The bis-Triazoline-dione is very soluble in polar solvents to give bright red solutions, but decomposes in two hours in dimethyl sulfoxide, one hour in dimethyl formamide , and decomposes in one and one-half hours with formation of a tan precipitate in tetrahydrofuran. It is also decomposed in less than fifteen minutes by wet acetone. The bisTriazoline-dione was found to be stable for over forty-

PAGE 15

12 eight hours when dissolved in a 50/50 mixture of reagent grade acetone and ethyl acetate, thus all reactions involving BDTD were carried out in this solvent mixture. Since PhTAD undergoes the Diels-ene reaction readily 21 22 with the allyl system, Â’ the possibility was suggested for the formation of copolymers by reacting BDTD, which also forms compounds by the Diels-ene pathway, with compounds that contain more than one allyl group. To investigate this possibility, BDTD was reacted with 1 , 6-heptadiene , 24, diallyl ether, _25, triallylamine , 26 , diallylpropylamine , 27, diallyldimethylsilane , _28 , diallylmethylphenylsilane , 29, diallyldiphenylsilane , 30, and 2, 6-diallyl-3, 5-dimethoxyphenol , 31. The heptadiene , 24-, and the ether, 2_5, both reacted slowly, taking over twenty-four hours to decolorize an equimolar

PAGE 16

13 concentration of BDTD. The two amines ,26^ and,2_7, react instantaneously with an equimolar concentration of BDTD in acetone/ethyl acetate to form a thick white, insoluble precipitate. The diallylphenol , 31, took nineteen hours to react. The ether, _25, the amines , 26 , and, 27, and the phenol, 31 , gave products in the form of white solids which were insoluble in dimethylformamide , dimethyl sulfoxide, dichlorome thane, acetone, ether, benzene, hexane, and chloroform. These products could also be heated to 300° C. with no apparent effects. The heptadiene , 24-, also gave an insoluble product that would not melt below 300° C. , but would soften at 287° C. Infrared spectra of these compounds indicated that they were copolymers of BDTD with the diallyl compounds and not a homopolymer of BDTD, a portion of which could be recovered in each case. It appears that the BDTD unit is capable of conferring a high degree of thermal stability to the copolymers that it forms. Since all of the BDTD copolymers were insoluble, model compounds were prepared to be used in nuclear magnetic resonance studies to help determine the structure of the copolymers. This was done for all of the diallyl compounds mentioned above, except for the diallylphenol and the triallylamine, by reacting them with two equivalents of PhTAD. The products of these reactions , 3^, 3_3, and, 34, were readily purified by crystallization from chloroform, and soluble in solvents such as acetone and dichlorome thane . Mass spectra.

PAGE 17

14 O 3 1 a/-C 2 H 1 3 3 C // t X 3t O + X infrared spectra, nuclear magnetic spectra, and elemental analysis indicated that the compounds ,32:, 33, and, 34, were 2:1 adducts formed by a Diels-ene reaction of PhTAD on each of the allyl groups. An adduct was not obtained in the reaction of PhTAD with 2 , 6-diallyl-3 , 5-dimethoxyphenol , 31 , because the PhTAD was decomposed by the presence of the hydroxyl group. This was confirmed by the reaction of PhTAD with 3,5dimethoxyphenol , 35 , which gave immediate decolorization of the PhTAD solution. BDTD however, shows no change when added to a solution of three equivalents of 3 , 5-dimethoxyphenol dissolved in a 50/50 mixture of acetone and ethyl acetate, and allowed to sit for forty-eight hours. Since BDTD should undergo the same Diels-ene reaction that PhTAD does, the repeat units in the copolymers should 35 ~

PAGE 18

15 have structures that are analagous to the corresponding model compounds . Cross-linking may be expected by reaction of the Triazolinedione unit with the vinyl structure formed in the copolymer, 36 , by the Diels-ene reaction, since studies by jo on Turner, Guilbault, and Butler, and by Wagener, show that both PhTAD and BDTD react readily with a series of vinyl compounds. This type of cross-linking probably does not occur in the copolymers, for the compound, 37, can be allowed to sit for forty-eight hours in a solution of PhTAD dissolved in methylene chloride with no change in the elemental analysis of the recovered adduct, 37, or in the nuclear magnetic resonance spectrum.

PAGE 19

16 The reactions of BDTD with the silicon compounds , 28 , 29 , and, .30, did not produce insoluble precipitates as did the other diallyl compounds. Instead, these compounds reacted to give an insoluble film which covered the inside of the reaction vessel. All the films produced were insoluble in dimethyl sulfoxide, dimethylformamide , acetone, ethyl acetate, methylene chloride, chloroform, ether, and hexane. They were partially soluble in a solution made by dissolving chromic acid in concentrated sulfuric acid. The films did differ in their mechanical properties. The film produced by the reaction of BDTD, 12 , and diallyldimethylsilane,2_8, was opaque and could be lifted off the glass surface of the reaction vessel in the form of rubbery sheets, which were flexible but had a very low shear strength. This compound had a softening point of 204° C. and turned a transparent, dark red color at 270° C. This decomposition product was very hard and upon subsequent heating to 300° C. showed no further change. The films formed by the reaction of BDTD with diallylmethylphenylsilane , 29^, and of BDTD with diallyldiphenylsilane , 30, were both a transparent gold color. Both of these films were strong and inflexible. They also adhered strongly to the glass of the reaction vessel and could not be removed as sheets as in the case of the diallyldimethyl copolymer, but instead had to be chipped off. The hardness of these films was approximately that of ice of the same thickness. The thickness of the polymer coating

PAGE 20

17 was measured as being between 0.5 mm and 1.0 mm for both compounds. The two copolymers do differ in their thermal properties. The product of BDTD and diallylmethylphenylsilane,_29, softened at 255° C. and then decomposed to the transparent red compound described earlier at 270° C. , while the product of BDTD and dial lyldiphenylsilane , 30, softened at 262° C. and decomposed at 270° C. to the same transparent red compound. The rates of reaction of the silicon compounds ,28,29, and,_30, with BDTD showed a progression. Diallyldimethylsilane, 2_8, reacted the fastest, taking one hour to decolorize a solution containing one equivalent of BDTD. Diallylmethylphenylsilane gave the next fastest rate, taking three hours to decolorize one equivalent of BDTD, while diallyldiphenylsilane gave the slowest reaction, taking four hours to decolorize the BDTD solution. This progression of rates is probably due to the added steric hinderance of the phenyl group compared to the methyl group. There is a soluble product left in the acetone/ethyl acetate solvent in each of the reactions of BDTD with the silicone compounds . This product can be recovered by dripping the acetone/ethyl acetate solution into a ten-fold excess of hexane. In each case, this process gives a dispersion in which the droplets adhere to any surface present in the flask and cover the surface with a yellow film. These films are soluble in polar solvents and can be crys-

PAGE 21

18 tallized from chloroform to give bright yellow crystals. These crystals showed the same changes in their physical properties with increasing temperature as did the corresponding insoluble compounds. The soluble fractions had the same infrared spectra and elemental analysis as did the corresponding insoluble compounds, thus they can be characterized as being the low molecular weight fractions of the insoluble polymers. Nuclear magnetic resonance spectra were taken of these soluble compounds, and they, along with the infrared spectra and elemental analysis of the insoluble films, support the presence of repeat units formed by a 1:1 Diels-ene reaction between the triazoline-dione units on BDTD with the allyl groups of the silane compounds.

PAGE 22

19 C. Reaction of PhTAD with Diallydialkylsilanes PhTAD, 1_, was reacted with diallyldimethylsilane , 28 , diallylmethylphenylsilane , 29, and with diallyldiphenylsilane,.30. These reactions showed a progression of rates f with the dimethyl compound, 2_8, and the methylphenyl compound,^, decolorizing a solution of two equivalents of PhTAD in methylene chloride, in less than five minutes. The diphenyl compound, 30 , required two hours and fifteen minutes to decolorize the same PhTAD solution. This was to be expected after the results of the reactions of these same silicon compounds with BDTD. Once again the steric hinderance of the two phenyl groups slows the reaction rate. The products of these reactions with PhTAD were recovered by dripping the reaction mixture into a ten-fold excess of hexane with stirring. This procedure resulted in the form of a precipitate obtained from each mixture. These precipitates were then filtered, dried and recrystallized from chloroform. The crystallization gave bright yellow, granular crystals in each case. The results of elemental analysis and nuclear magnetic resonance spectra, did not agree with the expected structure, 38.

PAGE 23

20 A sample of all three compounds was submitted for mass spectral analysis, and the resulting spectra indicated a cyclic structure ,_39, from the molecular weights and the splitting patterns. This cyclic structure agrees with the results of the elemental analysis and the nuclear magnetic resonance spectra. Reaction of PhTAD with allyltrimethylsilane , 40 , gave a product, 41, whose elemental analysis indicated it to be a 1:1 adduct as was expected. However, the nuclear magnetic resonance spectra of this compound shows the unambiguous pattern of an allyl group that is no longer attached to the silicon atom. The structure, AT, was assigned to this compound. This structure is supported by the splitting patterns found in the mass spectrum of this compound. C Hi

PAGE 24

21 This compound is not cyclic, but the structure infers that there was either a cyclic transition state or a cyclic intermediate involved in its formation. A possible transition state is the six center transition state of the HI Diels-ene reaction, except in this case an Si atom is abstracted instead of an H atom. This reaction is probably facilitated by the possible interaction of the non-bonding electrons of the nitrogen with the empty d-orbitals of the silicon. Because of these d-orbitals, the mechanism might not be concerted, but may rather involve an intermediate, 42 , in which loss of the Si from the carbonium ion would be preferred to loss of a proton.

PAGE 25

22 Application of this second possibility to the reaction of PhTAD with the diallyldialkylsilane compounds, yields a tentative mechanism for the formation of the products observed. This mechanism is shown in Scheme III. 3 ? The second intermediate ,45 , does not break the carbonsilicon bond as would happen in the first intermediate , 43 ,

PAGE 26

23 for the nitrogen introduced in the first step is in a position where the non-bonding electrons can help abstract a proton to form the double bond. At the same time the proton transforms the triazoline-dione unit into a good leaving group to regenerate the tetravalent silicon. The cyclic product, 39 , could still be formed if the intermediate product, 44, should undergo a normal Diels-ene reaction between the allyl group of the silicon and PhTAD to give the intermediate product, 46. This is shown in Scheme IV.

PAGE 27

24 The nitrogen of the newly added triazoline-dione unit could attack the silicon in an S n 2 manner to replace the triazoline-dione unit already bonded to the silicon atom to give ,47. The unstable intermediate , 47 , could then form the final cyclic product, .39, by loss of a proton. Silicon is known to be a center of attack for nucleophilic substitution 31 reaction, and the negative charge of the leaving triazolinedione unit could be somewhat stabilized by resonance with the oxygen of the adjacent carbonyl group , 47a . D. Reaction of PhTAD with Acetone In purifying some of the previously mentioned PhTAD adducts formed in 50/50 acetone-ethyl acetate solvent, a very soluble low molecular weight contaminant was found, whose increase in yield was directly proportional to the decrease in rate of the main reaction. The same compound could be obtained in high yield by allowing solutions of PhTAD in both 50/50 acetone-ethyl acetate and in dried acetone to sit until decolorization of the solution had occurred. The product could not be obtained from PhTAD in ethyl acetate. The product was an adduct of PhTAD and acetone, which formed in a very slow reaction. This compound was recovered by dripping the decolorized solution into a ten-fold excess of hexane. This resulted in a yellow oil which was purified by dissolving in methylene chloride and allowing crystals to grow. These crystals were bright yellow color and had a melting range of 126° 127° C. The

PAGE 28

25 nuclear magnetic resonance spectra of this compound, 48, gave two sharp singlets at x = 7.9 and x = 5.6, and a multiple t in the aromatic region at x = 2.5. These peaks had proton ratios of 3:3:5 respectively. Mass spectral splitting patterns, infrared spectra, and elemental analysis agree with the structure assigned, 4^8. A mechanism can be written for this reaction of PhTAD with the enol form of the acetone molecule, 49, which has the six center transition state common to the Diels-ene reaction. C C // 3 The slow rate of the reaction is due to the low concentration of the enol form. This reaction suggests the possibility of polymer formation between BDTD and the correct diketones. Cookson, Gilani and Stevens'^ reported formation of this compound, l-acetonyl-4-phenyl-l , 2 , 4-triazoline-3 , 5dione, m.p. 134 136°, in a similar manner; however, these authors did not suggest a mechanism for its formation.

PAGE 29

CHAPTER III EXPERIMENTAL A. General Information Nuclear magnetic spectra were taken on a Varian A60 spectrometer and infrared spectra were taken on a Beckman IR-8 spectrophotometer. Mass spectra were taken on a Model MS-30 mass spectrometer. Melting points were taken on a FisherJohns melting point apparatus and are reported in degrees centigrade uncorrected. Elemental analysis were completed by Atlantic Microlab Inc., of Atlanta, Georgia. All reagents used were obtained commercially and used as received except as noted. All solvents were commercial grade and used as received. B. Synthesis of 4-Phenyl-l , 2 , 4-Triazoli ne-3 , 5-Dione^ 3 Ethyl Carbazate Diethyl carbonate (1.80 mol., 200.0 g.) and 99% hydrazine hydrate (1.80 mol., 88.0 g.) were mixed together with continuous stirring for thirty minutes. This resulted in an exothermic reaction in which the two phases initially 26

PAGE 30

27 present combined to form one phase. The product of this reaction was distilled twice at 95° C. and 12 mm. This gave a yield of 130 g. (74%) of a white solid, mp 45-46° (Lit. 4 44-45.5°). o o l-Ethoxycarbonyl-4-phenylsemicarbizide Ethyl carbazate (0.62 mol., 60.0 g.) was dissolved in 200 ml benzene and cooled to 10° C. in a three-neck, 500 ml, round bottom flask fitted with an addition funnel, a mechanical stirrer, and a reflux condenser with a drying tube. Phenyl isocyanate (0.62 mol., 57.3 g.) was added dropwise through the addition funnel with stirring. This resulted in the formation of a white precipitate. After the addition was completed, the cold bath was removed and the mixture was refluxed for one half hour, during which time the white precipitate dissolved. When the solution was cooled to room temperature, the white precipitate reformed. This precipitate was filtered and washed twice with 75 ml portions of cold benzene. The yield was 108.6 g. (89.9%) of a white solid with a melting point of 153° C (Lit. 32 154°). 4-Phenyl Urazole l-Ethoxycarbonyl-4-phenylsemicarbazide (0.55 mol., 124.0 g.) was dissolved in 300 ml of hot 4M potassium hydroxide with stirring. The resulting light yellow solution was filtered and cooled. The solution was cooled in an ice-bath

PAGE 31

28 and acidified with 6M hydrochloric acid to give a large amount of white precipitate. The precipitate was collected by filtration and washed with enough cold water to remove any traces of acid. The washed precipitate was dried overnight in a vacuum oven yielding 71 g. (80.4%) of a white solid, mp 205-207° C (Lit. 32 206-207° C) . 4-Phenyl-l , 2, 4-Triazoline-3 , 5-Dione _ o 4-Phenyl urazole (3.43 x 10 mol., 6.0 g.) was placed in a 500 ml erlenmeyer flask with 100 ml dichlorome thane . This mixture was allowed to sit unstirred at room temperature while 4 drops of fuming nitric acid was added. There was a short induction period, after which the white urazole turned red and dissolved in the dichloromethane to give a red solution. The dichloromethane solution was filtered and evaporated by blowing a stream of compressed air over the surface of the solution. This resulted in a bright red crystalline substance which sublimed at 80° C and 1.0 mm. This material was used immediately upon preparation. Yield 5.6 g. (95.5%). C. Synthesis of Bis(p-3 , 5-dioxo-l , 2, 4-triazoline-4? f) ylphenyl) -methane Bis(4-isocyanatophenyl) methane was purified by vacuum distillation to give a clear colorless liquid which solidified on standing to white needle crystals. The

PAGE 32

29 isocyanate (61.7 g. , .247 mol.) was dissolved in 300 ml benzene. The resulting solution was added dropwise to a solution of ethyl carbazate (51.4 g. , .494 mol.) dissolved in 200 ml benzene and cooled sufficiently to keep the reaction temperature between 5° and 10° C. After the addition was completed, the solution was allowed to warm to room temperature. This resulted in a large amount of white precipitate which was filtered out and washed twice with cold 100 ml portions of benzene. The white precipitate was placed in a vacuum oven to dry overnight. This gave a white powder, mp 239-242° C (Lit. 26 240-244° C) . Yield 101 g. (91.2%). The bis-semicarbazide formed above (.22 mol., 101 g.) was dissolved in 500 ml 4M potassium hydroxide with stirring and heating to give a yellow-green solution. The solution was cooled to room temperature and acidified with 6M hydrochloric acid. This gave a large amount of white precipitate which was filtered out of the solution and washed with cold water. The washed precipitate was left in a vacuum oven to dry overnight. This gave a 94 g. (92.2%) yield of the bisurazole with mp 318° (Lit. 26 320°). The bis-urazole (4 g. , .011 mol) was placed in a 50 ml erlenmeyer with 25 ml dichlorome thane . This mixture was allowed to sit unstirred at room temperature while 4 drops of fuming nitric acid were added. This resulted in a reaction which formed a red solution. The dichloromethane was evaporated by blowing a stream of compressed air over

PAGE 33

30 the surface of the liquid. This gave 5.2 g. (87%) of the bright red bistriazoline-dione which decomposed at 326° C (Lit. 26 320°). Anal. Calc. c 17 H 10 N 6 O 4 ; C, 56.36; H, 2.98; N, 23.20 Found: C, 56.28; H, 3.01; N, 23.33 D. Synthesis of New Copolymers Reaction of BDTD with 1 , 6-hep tadiene BDTD (1.00 g. , 2.77 x 10 2 mol.) was dissolved in 30 ml 50/50 ethyl acetate/acetone cosolvent at room temperature. To the bright red solution which formed, 1 . 6-hep tadiene (.266 g. , 2.77 x 10 mol.) was added dropwise with stirring. There was no immediate color change observed. After two hours the solution had become orange in color, and was observed to be cloudy. 24 hours after the addition, there was a yellow layer of solid material covering the bottom of the reaction vessel. This solid was isolated, washed with dichlorome thane , and dried. After drying, the solid was observed to be brittle, and could be easily crushed to a yellow powder. This solid would not melt below 300° C, but would soften at 287° C. Infrared absorbances were observed (KBr) 3500 (m,b), 3300 (m) , 2980 (w) , 1800 (m) , 1730 (s,b), 1670 (w), 1600 (w), 1500 (m) , 1430 (m) , 1200 (w) , 1000 (w), 970 (m), 760 (w) cm" 1 . Anal . Calcd. for 1:1 copolymer C'24^'21^6^4 : 63.03; H, 4.59; N, 18.37. Found: C, 63.92; H, 4.48; N, 18.28.

PAGE 34

31 Reaction of BDTD with Diallyl Ether BDTD (1.00 g. , 2.77 x 10" 3 mol.) was dissolved in 20 ml 50/50 ethyl acetate/acetone cosolvent at room temperature. Diallyl ether (.271 g. , 2.77 x 10 3 mol.) dissolved in 10 ml 50/50 ethyl acetate/acetone , was added dropwise with stirring. After 43 hours, the reaction mixture was still a pale pink in color and had a heavy suspension of pink particles. These P ar ticles were so fine that they would pass through a medium glass frit and completely clog a fine glass frit. It was discovered that upon addition of 25 ml hexane, the particles would clump together and could be filtered with a coarse glass frit. After washing with acetone and drying, a white powder (1.12 g. , 88% yield) was obtained. This compound was heated to 300° C. with no visible change. Infrared absorbances were found at (KBr) 3500 (m) , 3300 (m) , 2990 (w) , 1800 (m), 1730 (s), 1640 (s), 1610 (s), 1600 (m) , 1510 (m) , 1440 (m), 1290 (s), 1200 (w) , 1000 (w) , 760 (w) cm" 1 . Anal. Calcd. for 1:1 copolymer C 23 H;l 9 N 6 0 5 C, 60.15; H, 4.14; N, 18.29. Found: C, 60.23; H, 4.08; N, 18.36. Reaction of BDTD with Diallylpropylamine BDTD (1.00 g. , 2.77 x 10 3 mol.) was dissolved in 20 ml 50/50 ethyl acetate/acetone. To this, a solution of diallylpropylamine (.377 g., 2.77 x 10” 3 mol.) in 10 ml 50/50 ethyl acetate/acetone , was added dropwise with stirring. The reaction was instantaneous, resulting in decolorization of

PAGE 35

32 the red BDTD solution and formation of a heavy, white precipitate. Yield of white powder after washing and drying was 1.31. g. (92.4%). This powder could be heated to 300° C. with no visual change. Infrared absorbances were found at (KBr) 3500 (m) , 3350 (m) , 3000 (w) , 1810 (m) , 1740 (s) , 1600 (w), 1500 (m), 1440 (m) , 1300 (s) , 1220 (s) , 1200 (m) , 1160 (m), 1050 (m), 1000 (w) , 770 (w) . Anal. Calcd. for 1:1 copolymer C 26 H 26 N 7°4 C ’ 62 -42: H, 5.20: N, 19.59: 0, 12.79. Found: C, 62.54; H, 5.28; N, 19.73. Reaction of BDTD with Triallylamine BDTD (1.5 g. , 4. 66 x 10 ^ mol.) was dissolved in 30 ml 50/50 ethyl acetate/acetone. To this was added triallylamine (.377 g. , 2.77 x 10 3 mol.) dissolved in 10 ml 50/50 ethyl acetate/acetone . The amine solution was added dropwise with stirring at room temperature. This resulted in instantaneous decolonization of the red BDTD solution and immediate formation of a white clump of solid material. This clump had the consistency of dried mud while still under the solvent and could be crushed easily with a stirring rod to a white powder. After washing with acetone and drying, the yield was 1.83 g. , 95.7%. This material would darken at 224° C, but still had not softened at 300° C. Infrared absorbances were found at (KBr) 3500 (m) , 3250 (m) , 3000 (w), 1800 (m), 1730 (s) , 1600 (w) , 1500 (m) , 1420 (m) ,

PAGE 36

33 1360 (s), 1280 (s), 1200 (w) , 1100 (m) , 1020 (w) , 750 (w) . Anal. Calcd. for 1:1 copolymer ^g^N-^Og: C, 61.64; H, 4.71; N, 19.96; 0, 13.69. Found: C, 61.70; H, 4.56; N, 20.13. r Reaction of BDTD with 2 , 6-diallyl-3 , 5-dimethoxyphenol BDTD (1.00 g. , 2.77 x 10 ^ mol.) was dissolved in 20 ml 50/50 ethyl acetate/acetone. 2 , 6-diallyl-3 , 5-dimethoxyphenol (.651 g. , 2.77 x 10 mol.) was dissolved in 10 ml 50/50 ethyl acetate/acetone , and this was added dropwise to the BDTD solution with stirring at room temperature. After a reaction time of nineteen hours, the solution had changed from a bright red color to a pale yellow color with a waxy white substance covering the bottom of the flask. This material was isolated by decanting the liquid of, adding fresh acetone and grinding the material under acetone. This procedure was repeated twice with 15 ml portions of acetone and one 15 ml portion of di chlorome thane . This treatment turned the white wax to a white powder, which was allowed to air dry. Yield 1.06 g. (64.2%). This powder was heated to 300° C. with no visible change. Infrared absorbances were found at (KBr) 3600 (w) , 3300 (m) , 2980 (w), 2850 (s) , 1950 (m) , 1810 (m) , 1730 (s) , 1640 (s) , 1620 (s), 1590 (m), 1500 (m) , 1430 (m) , 1410 (m) , 1200 (w) , 1000 (w), 840 (m), 760 (w) cm" 1 . Anal . Calcd. for 1:1 copolymer: 62.54;

PAGE 37

34 H, 4.53; N, 14.11; 0, 18.81. Found : C, 62.35; H, 4.59; N, 14.34. Reaction of BDTD with Diallyldimethylsilane Diallyldimethylsilane (.388 g. , 2.77 x 10 -3 mol.) was weighed into a flask containing 10 ml 50/50 ethyl acetate/ acetone. To this solution, another solution consisting of BDTD (1.00 g. , 2.77 x 10 3 mol.) dissolved in 20 ml 50/50 ethyl acetate/acetone was added dropwise, at room temperature with stirring. Midway through the addition, the reaction mixture was red in color, but had started to turn opaque. One hour after the addition had been completed, the mixture had turned a light golden yellow and a film was observed covering the entire inside surface of the reaction vessel up to the solvent level. The solvent was decanted off and the film allowed to dry. The film was opaque and did not adhere to the reaction vessel, instead it could be stripped off in flexible sheets. These sheets were insoluble in all solvents tried and only partially soluble in C O^/I^SO^ The film was washed in acetone and dried. Yield 1.15 g (83.0%). Softened at 204° C. , turned dark red at 270° and showed no further change at 300° C. Infrared absorbances were found at (KBr) 3500 (m) , 3330 (m) , 3000 (w) , 1800 (m), 1750 (m) 1670 (w) , 1500 (m) , 1410 (m) , 1260 (s), 1200 (m), 1000 (w), 950 (m) , 840 (s) , 760 (w) cm -1 . Anal. Calcd. for 1:1 copolymer C 25 H 25 N 6°4 Si: C,

PAGE 38

35 59.89; H, 4.99; N, 16.75; 0, 12.76; Si, 5.60. Found: C, 59.84; H, 5.01; N, 16.40. Reaction of BDTD with Diallylmethylphenylsilane Diallylmethylphenylsilane (.560 g. , 2.77 x 10'^ m) was weighed into a flask containing 10 ml. 50/50 ethyl acetate/acetone. To this solution another solution containing BDTD (1.00 g. , 2.77 x 10 ^ m) dissolved in 20 ml 50/50 ethyl acetate/acetone was added dropwise with stirring. One hour after addition the mixture was still red, but a film could be seen growing on the side of the reaction vessel. After six hours the solvent was poured off and the film allowed to air dry. After drying this film was found to adhere strongly to the glass vessel, but could be chipped off. Yield 1.35 g. (86.6%). Infrared absorbances were found at (KBr) 3500 (m) , 3300 (m) , 3000 (w) , 1820 (m) , 1750 (m), 1670 (m), 1630 (m) , 1490 (m) , 1430 (m) , 1260 (s), 1200 (w), 1130 (s), 1000 (w) 970 (m) , 830 (s), 760 (w) cm' 1 . Anal. Calcd. for 1:1 copolymer ^29^27^6^4^ 1: C, 63.17; H, 4.90; N, 15.20; 0, 11.6; Si, 5.09. Found: C, 63.22; H, 4.87; N, 15.37. Reaction of BDTD with Diallyldiphenylsilane Diallyldiphenylsilane (.731 g., 2.77 x 10'^ mol.) was weighed into a flask containing 10 ml 50/50 ethyl acetate/ acetone. To this solution, another solution consisting of BDTD (1.00 g. , 2.77 x 10 ^ mol.) dissolved in 20 ml 50/50

PAGE 39

36 ethyl acetate/acetone was added dropwise with stirring at room temperature. A film was noticed on the sides of the flask but its growth was much slower than with the other two diallylsilanes . After six hours the solvent was poured off and the film allowed to air dry. This film adhered strongly to the sides and bottom of the flask. Yield 1.47 g (84.9%). M.P.: Softens 262° C. , decomposes 270°C. Infrared absorbances were found at (KBr) 3500 (m) , 3300 (m) , 2980 (w), 1810 (m), 1730 (s), 1600 (m) , 1630 (s), 1510 (m) , 1430 (m), 1220 (m), 1125 (s), 1000 (w) , 970 (m) , 750 (w) . Anal . Calcd. for 1:1 copolymer C-^I^gNgO^Si ; C, 66.56; H, 4.75; N, 13.69; 0, 10.4; Si, 4.58. Found: C, 66.43; H, 4.70; N, 13.79. E. Formation of PhTAD Adducts Reaction of PhTAD with Acetone 4-Phenyl-l, 2 , 4-triazoline-3 , 5-Dione (,500g., 2.86 x _3 10 mole) was dissolved in 25 ml of acetone (reagent grade) which had been dried overnight over molecular sieves. The resulting bright red solution was allowed to react for 24 hours at room temperature. At the end of this period the now pale yellow solution was dripped into a 10-fold excess of hexane with stirring to give a golden oil which sank to the bottom of the hexane. The hexane was decanted and the 011 purified by dissolving in methylene chloride and allowing crystals to grow. These were recrystallized from methylene chloride to give bright yellow, flat diamond shaped

PAGE 40

37 crystals with a melting range of 126° 127° C. Nuclear magnetic resonance signals were observed at (CDCl^) 2.5 (m,5), 5.6 (s,2), 7.9 (s,3) t. Mass spectra data indicated the molecular weight to be 233 with major splitting pattern peaks at m/e 191, 190, 177, 119, 91, 77, 57, 43. Anal . Calcd. for 1:1 adduct C^H N^O^: C, 56.67; H, 4.71; N, 18.02; 0, 20.59. Found: C, 56.70; H, 4.68; N, 18.11. Reaction of PhTAD with Allyltrimethylsilane PhTAD (1.50 g. , 8.58 x 10"^ mole) was dissolved in 25 ml dichloromethane , to give a bright red solution. This was added dropwise to a solution of allyltrimethylsilane (.978 g., _ 3 8.58 x 10 mole) in 10 ml dichloromethane with stirring. The red PhTAD solution decolorized immediately upon entering the silane solution. The resulting solution was dripped into 350 ml of hexane. Evaporation of the hexane gave a thick oil. This was purified by dissolving in chloroform and adding enough hexane to induce crystallization. Yield, 1.81 g. (73.1%). Nuclear Magnetic resonance signals were observed at (CDCl^) <5 0.18 (s , 6) , 6 4.20 (d,2), 6 5.33 (m, 2) , 6 6.0 (m,l), 6 7.46 (m,5). Mass spectral data gives parent peak at 289 with major splitting pattern peaks at:. 274, 234, 217, 200, 189, 177, 120, 91, 77, 73, 41. Anal. Calcd. for 1:1 adduct C-^H2gNg02Si ; C, 58.13; H, 6.57; N, 14.52; 0, 11.06; Si, 9.71. Found: C, 58.62; H, 6.43; N, 14.30.

PAGE 41

38 Reaction of PhTAD with Diallyldimethylsilane PhTAD (1.695 g., 9.69 x 10 ^ mole) was dissolved in 20 ml of 50/50 acetone/ethyl acetate to give a bright red solution. A solution of diallyldimethylsilane (.678 g. , _ 3 4.85 x 10 mole) in 10 ml of 50/50 acetone/ethyl acetate was added dropwise with stirring at room temperature. The reaction was slightly exothermic. After the addition was complete, the mixture was still bright red but showed some cloudiness. After allowing to sit at room temperature for 24 hours, the solution was added dropwise with stirring to 300 ml of hexane to give a viscous orange oil. The oil was crystallized by grinding in a mortar and pestle with fresh hexane and drying under vacuum. The resulting fine orange powder was recrystallized from chloroform. Yield .858 g. (64.87o). M.P. Softens at 62° C. , Decomposes with evolution of gas at 75° C. Nuclear magnetic resonance signals were observed at (d^-acetone) <5 0.28 (m,6); 6 4.30 (m,2); 6 5.32 (m, 1) ; 6 5.92 (m,l); 6 7.52 (m,5). Molecular weight from mass spectral data: 273. Splitting pattern peaks at; 230, 217, 200, 189, 177, 160, 153, 139, 132, 120, 119, 100, 91, 83, 77. Anal. Calcd. for 1:1 adduct , 39 , 0 ^ 2 ^x 5 ^ 302 ^! : 0, 57.13; H, 5.49; N, 15.37; 0, 11.70; Si, 10.28. Found: C, 56.98; H, 6.01; N, 15.44.

PAGE 42

39 Reaction of PhTAD with Diallylmethylphenylsilane PhTAD (.558 g., 3.19 x 10 ^ mole) was dissolved in 40 ml of dichlorome thane and diallylmethylphenylsilane -3 (.215 g. , 1.06 x 10 mole) was weighed directly into the solution. After allowing to sit at room temperature for 24 hours, this was dripped into 400 ml hexane at room temperature with stirring, to give a white precipitate which agglomerated on stirring. This precipitate was filtered, washed with hexane and purified by redissolving in dichlorome thane and adjusting the solubility be adding enough hexane to initiate crystallization. Yield .282 g. (79.4%). M.P. 94-96° C. Nuclear magnetic resonance signals were observed at (D^-acetone) : 6 0.52 (m,3); <5 4.20 (m,2); 6 6.20 (m,l); 6 6.62 (m,l); 6 7.45 (m,10). Molecular weight from mass spectral data; 335. Splitting pattern peaks at; 322, 293 (very small), 217, 202, 200, 189, 177, 174, 160, 145, 132, 121, 120, 91, 77. Anal. Calcd. for compound, 39 , : C 18 H 17 N 3°2 Si: C > 64.47; H, 5.07; N, 12.52; 0, 9.54; Si, 8.38. Found: C, 64.73; H, 4.97; N, 13.03. Reaction of PhTAD with Diallvldiphenylsilane PhTAD (.500 g. , 2.86 x 10 ^ mole) was dissolved in 40 ml of dichloromethane and diallyldiphenylsilane (.377 g., 1.43 x 10 mole) was weighed directly into the solution. After allowing to sit for 24 hours at room temperature.

PAGE 43

40 this was dripped into 400 ml hexane at room temperature with stirring. This results in a fine white precipitate which clumps together on stirring. This precipitate was collected by filtration, washed and purified by redissolving in dichlorome thane and adding hexane to induce crystallization. Yield .402 g. (70.9%). M.P. 102 103.8° C. Nuclear magnetic resonance signals were observed at (Dg-acetone) 6 4.26 (m,2); 6 6.35 (m,l); 6 6.72 (m,l); 6 7.38 (m,15). Molecular weight from mass spectral data: 397. Splitting pattern peaks at; 355, 277, 236, 224, 217, 177, 120, 119, 105, 91, 77. Anal. Calcd. for compound, 39, : C 23^19^3®2^ : 69.52; H, 4.78; N, 10.57; 0, 8.05; Si, 7.07. Found: C, 69.98; H, 4.39; N, 10.93. Reaction of PhTAD with Diallylether PhTAD (1.882 g. , 1.07 x 10 2 mole) was dissolved in 30 ml of 50/50 ethyl acetate/acetone to give a bright red solution. Diallylether (.351 g., 0.35 x 10 -2 mole) was added and the reaction mixture allowed to sit for 24 hours at room temperature. At the end of this time, the mixture was still a bright red, but lighter in color than the original PhTAD solution. The mixture was dripped into 300 ml hexane to give a pinkish white powder which was electrostatic on drying. This was purified by recrystallization from acetone. Yield 1.38 g. (88.2%). M.P. Behavior: De-

PAGE 44

41 composes at 93.4° C. with evolution of gas. Nuclear magnetic resonance signals were observed at (D^-acetone) : 6 4.22 (m, 2) ; 6 5.00 (m,l); 6 5.82 (m,l); 6 7.36 (m,5) • f 6 8.5 (very broad, 1). Molecular weight from mass spectral data: 448. Splitting pattern peaks at: 271, 231, 215, 203, 190, 176, 146, 120, 119, 93, 77, 69, 43. Anal, Calcd. for 2:1 adduct: ^20^20*^6^5 : ^ * 58.95; H, 4.46; N, 18.74; 0, 17.85. Found: C, 59.22; H, 4.50; N, 18.94.

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REFERENCES CITED 1. J. Thiele and 0. Stange, Ann. , 283 , 1 (1894). 2. R.C. Cookson, S.S.H. Gilani, and I.D.R. Stevens, Tetrahedron Lett. , 615 (1962). 3. B.T. Gillis and J.D. Hagarty, J. Org. Chem. , 32, 330 (1967). ~ 4. J. Sauer and B. Schroder, Ber. , 100 , 678 (1967). 5. F. Yoneda, K. Suzuki, and Y. Nitta, J. Amer. Chem. Soc. , 88, 2328 (1967). 6. J.C. Stickler and W.H. Pirkle, J. Org. Chem., 31, 3444 (1966). 7. J.C. Stickler, Ph. D. Dissertation, University of Illinois, 1971, p. 4. 8. A.J. Solo, H.S. Sachdev, and S.S.H. Gilani, J. Org. Chem., 30, 769 (1965). 9. S.S.H. Gilani and D.J. Triggle, J. Org. Chem., 31, 2397 (1966). 10. J. Sauer, Angew, Chem. , (IE) 6, 26 (1967). 11. A.B. Evnin, R.D. Miller, G.R. Evanega, Tetrahedron Lett., 5863 (1968). 12. D.M. Lemal and J.P. Lokensgard, J. Amer. Chem. Soc. , 88, 5934 (1966). 13. A.G. Anastassion and R.P. Celluca, Tetrahedron Lett., 911 (1970). 14. C.M. Anderson, J.B. Bremmer, T.W. McCay, and R.N. Warrener, ibid, 1255 (1968). 42

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43 15. R. Breslow, J. Hoffman, M. Jacob, Jr., J. Amer. Chem. Soc. , 94, 2110 (1972). 16. R.C. Cookson, S.S.H. Gilani and I.D.R. Stevens, J. Chem. Soc. , 1905 (1967). 17. G.B. Butler, L.J. Guilbault and S.R. Turner, Polym. Lett. , 9, 113 (1971). 18. S.R. Turner, L.J. Guilbault and G.B. Butler, J. Org. Chem. , 36, 2838 (1971). 19. L.J. Guilbault, S.R. Turner and G.B. Butler, Polym. Lett. , 10, 1 (1972). 20. K.B. Wagener, Ph. D. Dissertation, University of Florida, p . 60 . 21. D.J. Pasto and A.F.T. Chen, Tetrahedron Lett., 2995 (1972) . 22. W.H. Pirkle and J.C. Stickler, Chem. Comm. , 760 (1967). 23. J.K. Stille, Fortsche. Hochpolymer Forsch. , 3 , 48 (1961). 24. W.J. Bailey, J. Economy and M.E. Hermes, J. Org. Chem., 27, 3295 (1962). 25. J.K. Stille and L. Plummer, J. Org. Chem. , 26, 4026 (1961) . 26. B. Saville, J. Amer. Chem. Soc. , 90 , 635 (1971). 27. S.R. Turner, Ph. D. Dissertation, University of Florida, p . 60. 28. K.B. Wagener, Ph. D. Dissertation, University of Florida, p. 53. 29. K.B. Wagener, ibid. , p. 43. 30. K.B. Wagener, ibid. , p. 49. Earbom, C. Organosilicon Compounds , 1960, Academic Press . 31.

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BIOGRAPHICAL SKETCH Wayne Eugene Ruch was bom in Pittsburgh, Pennsylvania on November 24, 1946. He graduated from Avonworth High School in June of 1964 and received his Bachelor of Science Degree from the Chemistry Department of Carnegie Institute of Technology in June of 1968. During his senior year of college, he was employed by the Gulf Oil Catalysis Research Group at Mellon Institute. The author was accepted for graduate studies at the Chemistry Department of the University of Florida for the fall of 1968 but was drafted to serve his country the following March. He served two years with the K-9 Corps of the U.S. Army, one year of which was spent as a tunnel dog handler with the 63 rd combat tracker platoon of the Americal Division, where he was awarded the Bronze Star and an Oak Leaf Cluster to the Bronze Star. At the end of his service he returned to his studies. In March of 1974 the author entered the employ of the Semiconductor Division of Harris Corporation as a senior engineer in the Materials Department. At present he is the engineer in charge of hard surface mask production. 44

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I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a master's thesis for the degree of Master of Science. 'tA x. fr) "George B. Butler Professor of Chemistry I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a master's thesis for the degree of Master of Science. Paul Tarrant Professor of Chemistry I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a master's thesis for the degree of Master of Science. Thieo E. Hogan Esch Asst. Professor of Chemistry This thesis was submitted to the Graduate Faculty of the Department of Chemistry in the College of Arts and Sciences and to the Graduate Council, and was accepted as partial fulfillment of the requirements for the degree of Master of Science. December, 1975 Dean, Graduate School