Synthesis of Polyspiroketals Containing Five-, Six-, Seven-, and Eight

30 Synthesis of Polyspiroketals Containing Five-, Six-, Seven-, and Eight-Membered Rings

Downloaded by UCSF LIB CKM RSCS MGMT on November 19, 2014 | http://pubs.acs.org Publication Date: August 12, 1982 | doi: 10.1021/bk-1982-0195.ch030

WILLIAM J. BAILEY, CHARLES F. BEAM, JR., EDMUND D. CAPPUCCILLI, IBRAHIM HADDAD, and ANGELO A. VOLPE University of Maryland, Department of Chemistry, College Park, MD 20742

Since the study of model compounds had shown that ketals containing five-, six-, seven-, and eight-membered rings could be formed in very high yields by heating a ketone or diketone with a diol in the presence of an acid catalyst with removal of the water that was formed by azeotropic distillation, these reactions were extended to produce a series of new analogous polyspiroketals. Furthermore since the formation of the intermediate hemiketal is not a stable product and it is necessary to proceed all the way to the ketal before a stable unit is formed, this reaction appeared ideal for the synthesis of soluble linear polyspiroketals containing only cyclicized structures. This reaction also represents a condensation polymerization analog of the free radical inter-intramolecular polymerization to produce linear polymers. Thus it was shown that linear soluble polymers could be prepared from the following polyfunctional materials: a five-membered ring -containing polyketal from 1,2,4,5-tetrahydroxy-cyclohexane and 1,4-cyclohexanedione; six-membered ring-containing polyketal from 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane, and 1,1,6,6-tetrakis(hydroxymethyl) cyclohexanone; six-membered ring-containing polyketal from 1,3-dihydroxyacetone, as well as 1,10-cyclooctadecanedione and pentaerythritol; a seven-membered ring -containing polyketal from 1,4-cyclohexanedione and 1,2,4,5-tetrakis(hydroxymethy1)– 00097-6156/82/0195-0391$06.00/0 © 1982 American Chemical Society

In Cyclopolymerization and Polymers with Chain-Ring Structures; Butler, G., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

392

POLYMERS WITH CHAIN-RING STRUCTURES


cyclohexane; and an eight-membered r i n g – containing p o l y k e t a l from 1 , 4 , 5 , 8 - t e t r a k i s ( h y d r o x y m e t h y l ) - t e t r a l i n and 1 , 4 - c y c l o hexanedione. A l t h o u g h the c o n d e n s a t i o n p o l y m e r i z a t i o n of a t r i f u n c t i o n a l o r t e t r a f u n e t i o n a l monomer w i t h a d i f u n c t i o n a l monomer, s u c h as t h e c o n d e n s a t i o n o f g l y c e r o l w i t h p h t h a l i c a n y d r i d e , w i l l u s u a l l y produce a h i g h l y c r o s s l i n k e d , i n s o l u b l e p r o d u c t , t h e r e a r e many e x c e p tions. J u s t as i n t h e c a s e o f i n t e r - i n t r a m o l e c u l a r free r a d i c a l a d d i t i o n p o l y m e r i z a t i o n , i f stable fiveor six-membered r i n g s can f o r m , a s o l u b l e polymer usually results. K e t a l f o r m a t i o n between a c y c l i c d i k e t o n e and a t e t r a o l i s a g o o d i l l u s t r a t i o n o f s u c h a r e a c t i o n (1,2,3)· The r e s u l t i n g s p i r o k e t a l p o l y m e r s w h i c h a r e d o u b l e - s t r a n d e d p o l y m e r s and a r e t h e r e f o r e r e l a t e d i n p r o p e r t i e s to l a d d e r p o l y m e r s are of a d d i t i o n a l i n t e r e s t because they have a h i g h degree of c h e m i c a l and t h e r m a l s t a b i l i t y s i n c e t h e y r e s i s t c h a n g e s i n m o l e c u l a r w e i g h t and b e c a u s e t h e y h a v e e x tremely h i g h m e l t i n g p o i n t s or g l a s s transitions s i n c e t h e y h a v e h i g h r e s t r i c t e d r o t a t i o n ( 4_) . A number of o t h e r s p i r o p o l y m e r s have been r e p o r t e d r e c e n t l y i n c l u d i n g p o l y s p i r o b e n z o t h i a z o l i n e s (5) , t h e c o n d e n s a t i o n p r o d u c t s o f d i a n h y d r i d e s w i t h t e t r a a m i n e s (6^), s p i r o p o l y a l l e n e s (7_) , and s p i r o t e t r a s u l f i d e s (JO . The k e t a l f o r m a t i o n i s an i d e a l r e a c t i o n f o r t h i s study s i n c e i t produces e i t h e r a s t a b l e s p i r o r i n g or no new b o n d a t a l l . The c o n d e n s a t i o n p r o c e e d s s t e p w i s e , but s i n c e the h e m i k e t a l i n t e r m e d i a t e i s u n s t a b l e , no c o n d e n s a t i o n w o u l d be e x p e c t e d t o t a k e p l a c e u n t i l the s t a b l e k e t a l i s formed.

o o ^c

/

C H

3 \ _ /

S 0

H

3 »

70%

xo< ta::>o o » - w° τ

c i s or trans

°

c o o c O

c i s , c i s o r t r a n s , trans

In the extension of the r e a c t i o n to polymers 1,2,4,5-cycloh e x a n e t e t r o l was prepared i n a 12% o v e r - a l l y i e l d from 1,4-cyclohexadiene by the o x i d a t i o n with osmium t e t r o x i d e . The meso (12/45) diastereomer o f ( c i s / c i s ) 1,2,4,5-tetrahydroxy-cyclohexane (15) was condensed w i t h 1,4-cyclohexanedione t o g i v e a 95% y i e l d of a c r y s t a l l i n e s p i r o polymer VI. T h i s m a t e r i a l d i d not melt, but was s o l u b l e i n hexafluoroisopropanol with an [η] of 0.056 d l / g (25°, h e x a f l u o r o i s o p r o p a n o l ) .

3 C Ç * 0 * cis/cis

lfc>OCCp( VI

We next became i n t e r e s t e d i n the p o s s i b i l i t y of extending t h i s to a seven-membered c y c l i c k e t a l . I t was immediately r e cognized that i f the y i e l d o f the c y c l i c compound were not n e a r l y q u a n t i t a t i v e , the r e s u l t i n g polymer would be c r o s s - l i n k e d . In our previous work (16) the c i s - and t r a n s - l , 2 - b i s (hydroxymethyl)cyclohexane were prepared. When e i t h e r the c i s - or t r a n s - d i o l was condensed w i t h 1,4-cyclohexanedione, a 92% y i e l d of the corresponding model compound was obtained.

az;i*o°^oc>coo

c i s or trans

c i s , c i s o r t r a n s , trans

Also i n our previous work, the t e t r o l , 1,2,4,5-tetrakis(hydroxymethyl) cyclohexane (17,18) o f unknown stereochemistry was obtained. When t h i s t e t r o l was condensed with cyclohexanone, a 92% y i e l d o f the b i c y c l i c k e t a l c o n t a i n i n g the seven-membered r i n g was obtained.



30.

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Polyspiwketah

E T AL.

397

When t h i s same t e t r o l was condensed with 1,4-cyclohexanedione i n η-butyl ether i n the presence of a t r a c e of £-toluenesulfonic a c i d , a n e a r l y q u a n t i t a t i v e y i e l d o f a white polymer V I I was obtained. T h i s m a t e r i a l d i d not melt, but was s o l u b l e i n hexaf l u o r o i s o p r o p a n o l and had an [η] o f 0.04 d l / g (25°, h e x a f l u o r o i s o p r o p a n o l ) . T h i s polymer V I I was found to be h i g h l y c r y s t a l l i n e by X-ray powder p a t t e r n and had a Τ % i n the DTA apparatus o f 400°. 1

HOCH

+ HOCH

/

Z

o A o ^ner H+ 99%

1

" "Υ Ύ Ύ Ύ ^ 0'

VII

χ

A very s i m i l a r polymer was prepared from t h i s same t e t r a k i s (hydroxymethyl) cyclohexane and 1,10-cyclooctadecadione. A white s o l i d was obtained i n a 93% y i e l d which was s o l u b l e i n hexa— f l u o r o i s o p r o p a n o l and s l i g h t l y s o l u b l e i n hot dioxane. I t was shown to be h i g h l y c r y s t a l l i n e by an X-ray powder d i f f r a c t i o n and d i d not melt. I t s [η] i n h e x a f l u o r o i s o p r o p a n o l was 0.062 d l / g (25°). The f a c t that these two polymers c o n t a i n i n g seven-membered s p i r o k e t a l s were h i g h l y c r y s t a l l i n e and s o l u b l e , i n d i c a t e s that the k e t a l formation proceeded i n e s s e n t i a l l y a q u a n t i t a t i v e manner. In order t o reduce the c r y s t a l l i n i t y o f the p o l y k e t a l an unsymmetrical c y c l i c diketone was prepared from 2,7-dihydroxynaphthalene. Reduction of the naphthalene nucleus w i t h Raney n i c k e l and hydrogen gave a 90% y i e l d o f the 2 , 7 - d e c a l i n d i o l , which on o x i d a t i o n w i t h chromic a c i d gave a 50% y i e l d o f the 2,7-decal i n d i o n e . When t h i s diketone was condensed w i t h the t e t r a k i s (hydroxymethyl) cyclohexane, an 89% y i e l d o f a white polymer V I I I was obtained which d i d not melt and was s o l u b l e only i n hexaf l u o ro isopropano1.

XXX

HOCH 2V ^V X

C H

2°

H

n - b u t y l ether ^


398


Since the seven-membered r i n g s formed so r e a d i l y to produce the k e t a l s , an i n v e s t i g a t i o n was undertaken to see i f e i g h t membered c y c l i c k e t a l s would form as r e a d i l y . A model compound was prepared from 1,8-bis(hydroxymethyl) naphthalene and c y c l o hexanone i n a n e a r l y q u a n t i t a t i v e y i e l d o f the c y c l i c k e t a l con t a i n i n g the eight-membered r i n g .

// \V-CH OH Downloaded by UCSF LIB CKM RSCS MGMT on November 19, 2014 | http://pubs.acs.org Publication Date: August 12, 1982 | doi: 10.1021/bk-1982-0195.ch030

2

V

\ //-

I t thus appears that a wide v a r i e t y o f t e t r o l s and c y c l i c diketones can be used to prepare a l a r g e v a r i e t y o f s o l u b l e p o l y s p i r o k e t a l s . I t appears that the r e a c t i o n can be made to go r e a d i l y when the k e t a l contains e i t h e r f i v e - , s i x - , seven-, or eight-membered r i n g s . Some o f the polymers c o n t a i n i n g the f i v e - , seven- and e i g h t membered r i n g s can, o f course, be considered to be a h y b r i d between ladder polymers and s p i r o polymers. An e f f o r t w i l l be made to see what other c y c l i c k e t a l s a r e u s e f u l f o r the f o r m a t i o n o f s p i r o polymers and what other types o f r e a c t i o n s besides the k e t a l formation w i l l produce s i m i l a r polymers. Experimental 7,14, 21, 26-Tetraoxatetraspiro [5. 2. 2. 2. 5. 2. 2. 2] hexacosane. Into a 3)0-ml, round-bottomed f l a s k equipped w i t h a magnetic s t i r r e r , a Dean-Stark trap and a r e f l u x condenser was added 2.04 g (0.01 mol) o f 1,1, 4, 4 - t e t r a k i s ( hydroxyme thy]) cyclohexane, mp 22322 4° [reported (l_2)rop 219-222°C], 2.16 g (0.022 mol) o f c y c l o hexanone, 0.1 g o f p - t o l u e n e s u l f o n i c a c i d , and 300 ml of benzene. A f t e r the mixture had been heated under r e f l u x u n t i l no more water c o l l e c t e d i n the Dean-Stark t r a p , the benzene was removed by d i s t i l l a t i o n under reduced pressure. The r e s u l t i n g s o l i d was d i s solved i n abs ethanol and t r e a t e d w i t h s e v e r a l grams o f de-



30.

BAILEY E T A L .

399

Polyspiroketals

c o l o r i z i n g c h a r c o a l . The volume o f the s o l u t i o n was reduced to 10-15 ml by h e a t i n g on a steam bath. When the mixture was cooled f o r 1 hr, c r y s t a l l i z a t i o n occurred. One r e c r y s t a l l i z a t i o n from a d i l u t e s o i n of ethanol gave 2.91 g (80%) o f 7,14,21,26-tetrao x a t e t r a s p i r o [5.2.2.2.5.2.2.2] hexacosane, mp 188°C. A n a l . Calcd f o r C H O : C, 72.48; H, 9.95; m/e, 364.2614. Found: C, 72.58; H, 9.87; m/e, 364.2616. An IR spectrum o f t h i s compound had n e i t h e r a h y d r o x y l a b s o r p t i o n a t 3400 cm~l nor a carbonyl a b s o r p t i o n a t 17 25 cm-1. P o l y s p i r o k e t a l I I I by the Reaction o f 1,4-Cyclohexanedione with 1,1,4,4-Tetrakis(hydroxymethyl)cyclohexane. A mixture o f 10. 2 g (0.0 5 mol) o f 1,1, 4,4-tetrakis( hydroxymethyl) cyclohexane, 5. 6 g (0.05 mol) o f 1,4-cyclohexanedione and 0. 5 g o f £-toluenes u l f o n i c a c i d was heated under r e f l u x i n 200 ml o f benezene (reagent grade) . A f t e r the mixture had been heated w i t h r a p i d s t i r r i n g f o r 5 b r , another 150 ml o f benzene was added and the mixture was heated u n t i l no f u r t h e r water was c o l l e c t e d i n the Dean-Stark t r a p . The hot mixture was f i l t e r e d through a Buchner f u n n e l , and the s o l i d was washed s e q u e n t i a l l y w i t h 400-ml p o r t i o n s of b o i l i n g benzene, methanol, carbon t e t r a c h l o r i d e , chloroform, and Ν,Ν-dimethylformamide. F i n a l l y the polymer was washed w i t h 200 ml o f benzene, a i r d r i e d , and then vacuum d e s i c c a t e d f o r 6 hours to g i v e 10.0 g (70%) o f polymer I I I which showed no l o s s of water a t 100°C and no change o f c o l o r u n t i l 400°C. Some shrinkage was observed t o s t a r t a t 37 0°C a n d m e l t i n g w i t h d e composition r e s u l t e d between 410-450°C. Anal. C a l c d f o r ( C H 0 ) : C, 68.54; H, 8.63. F o u n d : C, 6 8 . 3 8 ; H. 8.37. 1 6

2 4

4

r

A f t e r a 0.2-g sample was added to 40 ml of h e x a f l u o r o isopropanol, the mixture was s t i r r e d overnight and f i l t e r e d . A r e s i d u e o f approximately 2 mg remained u n d i s s o l v e d . An i r spectrum o f the vacuum d e s i c c a t e d sample showed t r a c e absorptions a t 3420 and 1699 cm" which was a t t r i b u t e d t o entrapped s t a r t i n g m a t e r i a l or end-groups on the polymer c h a i n . An i r spectrum o f the same sample although nondesiccated, showed a pronounced i n c r e a s e i n the hydroxyl a b s o r p t i o n a t 3420 cm~l i n d i c a t i v e of the hydroscopic nature o f the polymer. A d e t a i l e d i r (Nujol) spectrum contained the f o l l o w i n g ab s o r p t i o n s : 1360 (m), 1345 (m), 1270 (m), 1240 (w), 1225 (w), 1169 (m), 1144 ( s ) , 1132 (m), 1110 ( s ) , 1101 ( s ) , 1079 (m), 1059 (m), 1050 (m \ 1038 (m), 1025 (m), 988 (w), 977 (m), 948 (m), 929 (w), 908 ( s ) , and 891 (m) cm" . 1

1

7,14,21,25-Tetraoxatetraspiro[5.2.2.2.5.2.1.2] pentacosan23-one. Into a 500 -ml f l a s k equipped w i t h a magnetic s t i r r e r , a Dean-Stark trap and a r e f l u x condenser was added 2.04 g (0.01 mol) of 2 , 2 , 5 , 5 - t e t r a k i s ( h y d r o x w e t h y l ) c y c l o p e n t a n o n e , mp 142-143°C [reported (14) mp 143°C], 2.10 g (0.021 mol) o f cyclohexanone, 150 ml o f benzene and 0.1 g p - t o l u e n e s u l f o n i c a c i d . The mixture was



400


heated under r e f l u x u n t i l no more water was c o l l e c t e d i n a DeanStark t r a p . The mixture had a blue r e s i d u e which was removed by f i l t r a t i o n , and the f i l t r a t e was washed w i t h 10 ml o f a 5% sodium bicarbonate s o i n followed by 10 ml o f water. A f t e r the s o i n was d r i e d (MgS04), f i l t e r e d , and concentrated, the r e s i d u e was r e c r y s t a l l i z e d twice from abs ethanol to g i v e 2.62 g (72%) o f 7, 14,21,25-tetraoxatetraspiro(5.2.2.2.5.2.1.2)pentacosan-23-one, mp 198-199°C. Anal. Calcd f o r C21H32O5: C, 69.20; H, 8.85. Found: C, 69.06; H, 8.81. An IR spectrum of t h i s compound showed no hydroxyl absorpt i o n , and a carbonyl a b s o r p t i o n was noted a t 1698 cm~l. P o l y s p i r o k e t a l from 2,2,5,5-Tetrakis(hydroxymethyl)cyclopentanone and 1,4-Cyclohexanedione. A mixture c o n s i s t i n g o f 1.12 g (0.01 mol) o f 1,4-cyclohexanedione, 2.04 g (0.01 mol) of 2,2,5,5-tetrakis-(hydroxymethyl)cyclopentanone, 0.1 g o f £r t o l u e n e s u l f o n i c a c i d , and 300 ml of benzene were heated under r e f l u x w i t h s t i r r i n g u n t i l no more water was c o l l e c t e d i n a DeanStark t r a p . The time r e q u i r e d was approximately 12 hr. The hot mixture was f i l t e r e d through a Buchner funnel and the polymeric residue was washed w i t h 300-ml p o r t i o n s o f b o i l i n g benzene, methanol and carbon t e t r a c h l o r i d e . The r e s i d u e was then vacuum d e s i c c a t e d f o r s e v e r a l hours to y i e l d 2.07 g (74%) o f polymer, mp 370-395°C. Anal. Calcd f o r (C n çP ) : C, 64.27; H, 7.19. Found: C, 62.40; H, 7.16. An IR spectrum of t h i s polymer showed mere t r a c e a b s o r p t i o n f o r hydroxyl group a t 3400 cm-1. The carbonyl a b s o r p t i o n peak a t 1700 cm-1 had no shoulders. A d e t a i l e d IR (Nujol) spectrum contained the f o l l o w i n g a b s o r p t i o n s : 1700 ( s ) , 1321 (w), 1263 (w), 1239 (m), 1195-1201 (m), 1161-117) (w), 1138 ( s ) , 1109 ( s ) , 1060 (m), 1020 (w), 985 (w), 961 (m), 952 (m), 931 (m), 905 (m), 885 (w), 760 (m), 750 (m), and 713 (m) c u r l . cis, cis-2,3,10,11-1»stetramethylene-1,4,9,12-tetraoxadispiro-[4.2.4.2] tetradecane. Into a 50 -ml f l a s k were added 1.5 g o f c i s - 1 , 2 - c y c l o h e x a n e d i o l , 0.56 g o f 1,4-cyclohexanedione, 0.1 g o f p - t o l u e n e s u l f o n i c a c i d and 30 ml o f benzene. The contents of the f l a s k were heated under r e f l u x overnight during which time the t h e o r e t i c a l amount of water separated. A f t e r the mixture was cooled to room temperature, the benzene s o l u t i o n was washed with water. A f t e r the s o l u t i o n was d r i e d over sodium s u l f a t e , most o f the s o l v e n t was removed by evaporation. The s o l i d t h a t separated was c o l l e c t e d by f i l t r a t i o n and washed w i t h ether. A r e p e t i t i o n of t h i s process gave a second crop or a t o t a l o f 1.5 g (86%). The s o l i d which was r e c r y s t a l l i z e d from c h i l l e d ether melted a t 173-173.5°C.; IR: 2935 ( s ) , 2860 (m), 1450 (m), 1380 (m), 1300 (w), 1208 (m), 1187 (m), 1123 ( s ) , 1100 ( s ) , 1045 (m) 980 (m), 970 (m), 920 ( s ) , 890 (w), 857 (w), 825 (w), 675 (w), 468 (w) cm-1. Anal. Calcd f o r C H 0 . : C, 70.10; H, 9.10. Found: C, 70.20; 15

17^.27.

2

1 Q

5

n

o o

1 82 84



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Polyspiroketals

E T AL.

401

P o l y s p i r o k e t a l from meso (12/45) Diastereomer o f ( c i s / c i s ) 1,2,4,5-Cyclohexanetetrol and 1,4-Cyclohexanedione. Into a 50 -ml f l a s k equipped w i t h a magnetic s t i r r e r and capped w i t h a DeanStark t r a p , a r e f l u x condenser and a d r y i n g tube were added 0.148 g o f 1,2,4,5-cyclohexanetetrol, 0.112 g o f 1,4-cyclohexanedione and 50 ml of n - b u t y l ether. A f t e r the mixture was heated under r e f l u x f o r 2 hours,0.01 g o f p - t o l u e n e s u l f o n i c a c i d was added. Heating was continued overnight a t the end of which time the f l a s k was cooled t o room temperature and the r e s u l t i n g s o l i d was c o l l e c t ed by f i l t r a t i o n . A f t e r i t was washed w e l l w i t h water, acetone and ether, the s o l i d was d r i e d over P2O5 under 0.2 mm pressure at about 70°C f o r 24 hours. The dry polymer V d i d not melt, was s o l u b l e only i n h e x a f l u o r o i s o p r o p a n o l , and had an [η] of 0.056 dl/g. Calcd f o r (C H., Λ>ά)η C, 64.20; H, 7.14. Found: C, 63.70; H, 7.14. Polymer V I I from 1,4-Cyclohexanedione and 1,2,4,5-Tetrakis(hydroxymethyl) cyclohexane. Into a 100—>ml f l a s k equipped w i t h a mag. s t i r r e r , a Dean-Stark t r a p , a r e f l u x condenser and a d r y i n g tube were added 50 ml of dry n - b u t y l ether, 2.04 g o f 1,2,4,5tetrakis(hydroxymethyl)cyclohexane and 1.12 g o f 1,4-cyclohexa nedione. The s o l u t i o n - s u s p e n s i o n was heated under r e f l u x f o r 12 hours followed by the a d d i t i o n o f 0.1 g o f p - t o l u e n e s u l f o n i c a c i d . A f t e r the mixture was heated o v e r n i g h t , i t was cooled to room temperature. The mixture was f i l t e r e d w i t h s u c t i o n and the r e s u l t i n g s o l i d was washed w e l l w i t h n - b u t y l ether. A f t e r most o f the ether was removed, the s o l i d was washed w i t h water, acetone and f i n a l l y ether. The s o l i d , which was d r i e d over P2O5 and under 0.2 mm pressure, weighted 3.1 g (99%). The s o l i d was s o l u b l e only i n h e x a f l u o r o i s o p r o p a n o l and had an [η] of 0.04 d l / g at 25°c. The polymer was found to be c r y s t a l l i n e by X-ray and d i d not melt. Anal. Calcd f o r ( C ^ R ^ O ^ ) : C, 68.54; H, 8.63. Found: C, 68.30; H, 8.49. A p o r t i o n of the polymer V I I , which was r e f l u x e d i n h e x a f l u o r o isopropanol to t e s t f o r h y d r o l y s i s , was recovered unchanged as shown by IR, TGA and a n a l y s i s . The i n f r a r e d spectrum showed bands a t 2930 (m), 2865 (m), 1450 (w), 1370 (w), 1250 (w), 1120 ( s ) , 1057 (w), 1035 (m), 946 (w), and 928· (w) cm-1. The authors are g r a t e f u l to the Army O f f i c e o f ResearchDurham, the Goodyear T i r e and Rubber Company, and the Naval Surface Weapon Center f o r p a r t i a l support of t h i s work. T h i s paper i s dedicated to P r o f e s s o r George B. B u t l e r , who i n i t i a t e d a l l o f the i n t e r e s t and r e s e a r c h i n the f i e l d o f i n t e r i n t r a m o l e c u l a r p o l y m e r i z a t i o n , on the o c c a s i o n o f h i s 65th b i r t h d a y .

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Literature Cited 1. Bailey, W. J . ; Volpe, A.A. J. Polym. Sci., Part A-1 1970, 8, 2109-17. 2. Bailey, W. J . ; Hinrichs, R.I. Am. Chem. Soc., Div. Polym. Chem., Preprints 1970, 11(2), 500. 3. Bailey, W. J . ; Beam, C. F., Jr.; Haddad, I. Am. Chem. Soc., Div. Polymer Chem., Preprints 1971, 12, 169-74. 4. Bailey, W. J. in Bikalis, N. "Encyclopedia of Polymer Science and Technology" Vol. 8; John Wiley and Sons, Inc.: New York, NY, 1968; pp. 97-120. 5. Augl, J. M.; Wrasidlo, W.J. J. Polym. Sci., Part A-1 1970, 8, 63-66. 6. Hodgkin, J. H.; Heller, J. J. Macromol. Sci.-Chem. 1969, 3, 1067-71. 7. Rinehard, R. E. (Uniroyal, Inc.) Ger. Offen. 1,943,624 (Mar. 5, 1970); Chem. Abstr. 1970, 72, 101, 242x. 8. Tokarzewski, L.; Plonka, S. Polimery 1969, 14(12), 596; Chem. Abstr. 1970, 73, 25,925a. 9. Cohen, S.M.; Lavin, E. J. Appl. Polym. Sci. 1962, 6, 503-7. 10. Cohen, S. M.; Hunt, C. F.; Kass, R. E.; Markhart, Α. Η., J. Appl. Polym. Sci. 1962, 6, 508-11. 11. Butler, G. B.; Angelo, R. J. J. Am. Chem. Soc. 1957, 79, 3128-31. 12. Beam, C. F., Jr.; Bailey, W. J. J. Chem. Soc., C 1971, 2730-2. 13. Mannich, C.; Brose, W. Ber. 1923, 566, 833. 14. Ray, G. C. (Phillips Petroleum Co.) U. S. Patent 2,500,570 (Mar. 14, 1950); Chem. Abstr. 1950, 34, 5385. 15. McCasland, G. E.; Furtra, S.; Johnson, L. F.; Shoolery, G. N. J. Org. Chem. 1963, 28, 894. 16. Bailey, W. J.; Golden, H. R. J. Am. Chem. Soc. 1953, 75, 4780. 17. Bailey, W. J.; Fetter, E. J . ; Economy, J. E. J. Org. Chem. 1962, 27, 3469. 18. Longone, D. T. J. Org. Chem. 1963, 28, 1770. RECEIVED

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1982.


Synthesis of Polyspiroketals Containing Five-, Six-, Seven-, and Eight

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