11.L. WOLFROM, MADELINE S. TOYAND ALAXCHAXEY
G32x
[CGSTRIBUTIOS FROM
THE
DEPARTMEST O F CHEMISTRY
OF
VOl.
so
THEOHIO STATE UNIVERSITY]
Condensation Polymers from Tetra-0-acetylgalactaroyl Dichloride and Diamines1S2 13s 11.L. I\.OLFRORI, L~ADELINE S.T O YAND XLANC I L ~ N E Y RECEI\.EIIJL-1.Y 11,19-58 Polymers were obtained from the condensation of tetra-0-acetylgalactaroyldichloride with ethyleiiediamirie or piperazine with subsequent rencetylatioii. Deacetylation was efiected with probable hydrolytic degradation t o yield polymers containing 30-40 repeating units. These hydroxy polyamides were unstable t o both acid and basic media. Certain monomolecular amides and an ester were synthesized for comparative purposes.
The preparation of polymers containing carbo- tially deacetylated under the final basic conditions hydrate repeating units has been of considerable of the reaction. Reacetylation of these products interest in recent years. Haworth, Heath and afforded the fully substituted derivatives I1 and IV. Wggins3 reported the condensation of 1,G-diamino- The acetylated polymers were insoluble in the com1,G-dideoxy-di-0-methylene-D-mannitol with di-0- mon organic solvents. They dissolved in 50 to methylene-D-glucaric acid to afford a brittle poly- 80% sulfuric acid with degradation. The action of methanolic sodium methoxide on mer which could not be drawn. Somewhat later, SViggins4 reported the condensation of 1,2 : 5,6-di- the originally prepared polymers caused deacetylaanhydro-3,4-0-isopropylidene-~-mannitol with 1 , G - tion, polymers I11 and V being isolated in 3 0 4 0 % diamino-1,6-dideoxy-di-O-methylene-~-mannito1 to yields. These hydroxy polyamides dissolved with produce a polymer which exhibited fiber-forming degradation in anhydrous ethylenediamine and characteristics. Mehltretter and Melliesj have re- 5 0 - S O ~ o sulfuric acid and without chemical change ported the condensation polymerization of 2,4 : 3 5 in 507, lithium chloride. Intrinsic viscosities, [TI di-0-methylene-D-gluconicacid upon heating in = 0.13 deciliter per gram for I11 and 0.11 for V, pyridine containing benzoyl chloride. The acryl- were obtained in this latter solvent. Light scatterate and methacrylate esters6 and the allyl ethers' ing investigations on I11 afforded a minimum molecof a number of carbohydrates have been prepared ular weight of 5,500 or about 36 repeating units. and polymerized. The preparation of carbohy- Experimental difficulties in obtaining exact stoichidrate derivatives of polyvinyl alcohol and polyvin- ometry of the reacting species were probably reylamine have been studied.s The thermal conden- sponsible, in part, for the low molecular weights sation of methyl 2-deoxy-P-~-galactofuranoside has achieved. For example, a lY0 deviation from stoibeen shown to afford low molecular weight poly- chiometry would result in a maximum theoretical Mora and Wood1a have furnished details chain length of about 100 repeating units." Deviaof the synthesis of high molecular weight polysaco==c-~i charides arising from the thermal polycondensation HCOA~ of a-D-glucose under acid conditions. 1. Diamine The ease of synthesis of tetra-0-acetyl-galacta-+ AcOCH I royl (mucyl) dichloride (I) suggested that its reac1 2. Ac2O AcOCII tion with diamines or diols should be examined. C,H ,>s I This difunctional acyl halide should provide polyIiCOAc mers which could be deacetylated to the parent hydroxylic substance which should then be convertible c1 -c=o to other derivatives. The diamines, ethylenediamine and piperazinc ( 2 moles), were added a t 0" t o stirred suspensions of HCOAc I (1 mole) in benzene. The second mole of amine AcOCI-I was employed to combine with the hydrogen chloI ride liberated in the condensation and could be replaced by tertiary amines. High yields were obtained of polymeric products which had been par-
r
1
(1) This work was performed under contract, DA-33-0194rd-2025, between the U. S . Army Ordnance Corps (technical supervising agency, Ballistic Research Laboratories of Aberdeen Proving Ground) and T h e Ohio State L-niveriity H e m r c h Foundation (Project 675). ( 2 ) IJrom the 11 Sc. 'I h e 4 , \iil,mitted 1,y .\ladcline S 'I-\-, T h r Oliici State Tini\-ersity, l % i 7 , c i , m ; ~ l c r e infrared ilxctrti o i all neb\ c ~ , m p a u , ~ dms e thcrein I r c w T r e d . ( : 3 ) TV, S . Haworth, I< I. I I c a t h ;rnd 1.. I: JVisgin5, ./. Cht,n?. S u i . , l.i.7 ( 1 ~ ) L l I ! 'I!lW I : . L \iel!ie'~. THIS JOCKSXI,, 77, 11'7
u n o v s X j - , TEIISJor.~s.sr., 6 6 , 1623 ( l W 4 ) \Iichi-el .ind TT.. Fiimmelmnnn, X o f x r w i s s . , 42, 207 11 \:'. (;, 0 , i . r t . r i d 1: Sh ideh ;rnd .\I. Staccy, J . C'hc>ir. . \ t l , . . , :+S4
1:. (!i)
( 1 ' 1 i")
C1 I
I1 and 111, R = - N H C H ? C H , S H -
1.
L -c-* 1, I11 and 1-
IL' and r---, V , R = -S N\-~-
tions of this order could easily have arisen in the current work. The polymers were degraded in ethylenediamine solution as shown by viscosity changes (Fig. 1). The differences in the limiting viscosities obtained are probably the result of fractionation during ( I 1) F. \V, Rillnieyer, J I ., "Te*tiiiwk oi Pulymer Cheniistry," Interscience Publishers. I n c . , S e w T i i r k , S .T., 19.77, 1'. 181
TETRA-0-ACETYLGALACTAROYL DICHLORIDES AND DIAMINES
Dec. 5, 1958
6329
c
preparation of the various derivatives from the 0.30 \ original polymers. The low yields of the deacetylated polymers, I11 and V, prepared in strongly basic media, are probably due t o degradation effected by amide hydrolysis. Furthermore, the molecular weight of these materials, as determined by the light scattering method, is undoubtedly considerably lower than that of the polymers orig0.20 inally prepared. It recently has been shownI2 i; that the aldonamides are hydrolyzed more easily 9 c than are the unsubstituted amides. Therefore, in the present case, the degradation of the hydroxy polyamides might be expected to occur with greater ease than with the simple aliphatic polyamides. 0.10 The infrared spectra2 of the polymers and the various model compounds prepared (VI to I X ) fully confirmed the assignment of the polyamide structures, I1 to V. The model compounds are new substances : 1,l'-(tetra-0-acetylgalactaroy1)dipiperidine (VI), 1,l'-(galactaroy1)-dipiperidine 0 1 2 18 (VII), tetra-0-acetylgalactaric bis-(phenylhydraTime, hr. zide) (VIII), galactaric bis-(phenylhydrazide) (IX) Fig. 1.-Change of viscosity with time a t 25.0' in ethyland bis-(2-hydroxyethyl) tetra-o-acetylgalactarate. The analytical data obtained further sub- enediamine: 0, polymer V, c 0.5; 0 , polymer IV (not fully acetylated), c 1.0. stantiated the structures (I1to IX) assigned.
--.
C=O
NHNHC~HS
C=O
HCOR I ROCH
HCOR
ROCH
ROFH
I
HCOR
ROFH
I
HCOR
c=o N?
c=o
W
NHNHCsH5
VI, R=CH3C0 VII, R = H
VIII, R = C H B C O
IX,R = H
Nitration of the deacetylated polymers by various techniques13 failed to give well defined products and very low yields of unstable materials were obtained. It appears that acid media cause severe degradative hydrolysis of the polymers.
Experimental Preparation of Tetra-0-acetylgalactaroyl (Mucyl) Dichloride (I).-Galactaric (mucic) acid, 100 g., was refluxed for 2 hr. with 625 ml. of acetic anhydride containing 2.5 ml. of concd. sulfuric acid. T h e mixture was filtered hot and the filtrate cooled. T h e precipitate of tetra-0-acetylgalactaric acid which formed was collected by filtration, washed with anhydrous acetic acid and cold abs. ethanol, and recrystallized from boiling ethanol; yield 89 g., m . p . 242243 O , identical with the recorded v a 1 ~ e . l ~ A mixture of 45 g. of this acetate, 60 g. of phosphorus pentachloride and 450 g. of acetyl chloride was stirred a t room temperature. After 15 min., a clear solution resulted from which silky white crystals began t o separate. ,Ifter 1 hr., the separation was completed b y the addition of petroleum ether (b.p. 30-6OO). T h e solid tetra-0-acetylgalactaroyl dichloride was recovered by rapid filtration and (12) h f , L . lkrolfrom, I
