tlie visi.osit!.
the ~olutioiisdccreased ragidlJ- with time to :L limiting n l u e . A Xyh aqueous solution of lithium chloride was found t o be an unreactive solvent for the polymer 111. Solutions of the polymer were studied in Fenske viscometers. X plot o f the reduced viscosity (qep/c) against the specific viscosity ( q a p ) was linear and hxd negligible slope. Extrapolation to zero specific viscosity gave a n iutrinsic viscosity, of 0.12 tleciliter/g. Solutious of t h e polymer were also subjected t o a light scnttering molecular weight determination following the techniques and instrumentation employed b y Heilweil arid \-an \\'inkle.l~ Calculations were made as outlined by Flory." 111this manner tlie minimum molecular weight for polymer 111 was found t o be 8,500 or about 36 rtpcating units. 2 . Piperazine.-Piperazitie (300 mmol.), dissolved in 400 inl. of benzene, was added slowly under anhydrous conditions t o a stirred suspension of 43.3 E. (105 nimol.) of I in 300 ml. of benzene-at 0'. T h e stirring was c o n h u e d while t h e mixture warmed t o room temperature. Centrifugation afforded a white solid which was washed with benzene and ethanol. .Iportion of this polymer was acetylated to >-ield product I\', as described for t h e ethylenediamine polymer; yield 81(;&(basis I ) . ilnul. Calcd. for [CloH19~;206(CI-13CO),]n: C, 50.46; H , 5.61; S, 6.54;CH3C0, 40.1. Found: C , 50.10; H, 3.67; N. 6.55; CH,CO, 39.2. S o solvent was available t h a t did not degrade the polymer and no melting point was found; decomposition began 011 lieating above 250'. Another portion of t h e polymer, before acetylation, was treated with sodium in methanol as described above. T h e t1e:icetylated pol>-nier Y was again obtained in poor yield. A n a / . Calcd. for [ C I ~ H , & ~ O ~C, ] ~ 46.15; : H, 6.15; 9, 10.77. Found: C , 46.35; H, 6.19; X, 10.81. Tlic infrared spectra,2 thermal behavior and solubility pfoperties of 1- were similar in all respects t o t h e ethylenetlianiine analog 111. From viscosity studies in ,5OY0 aqueous lithiiun chloride an intrinsic viscosity, [ q ] ,of 0.11 deciliter/'g. \vas derived. Attempted Nitration of Po1vmers.--A variety of nitration t c c l ~ n i q u & ~were ~ applied t o various preparations of the deacet)-latcd polymers. In no case was a satisfactor), J-ielrl obtdined; t h e products appeared t o be mainly rvatersoluble or were decomposed by water. Synthesis of Model Compounds. 1. 1,l'-(Tetra-0acetylgalactaroy1)-dipiperidine (VI).-Piperidine (16.2 ml., 164 niiiiol.) mas added slowly t o a stirred suspension of 16.3 g- .- (.30 mtnol.) of tetra-0-acetylgnlactaro!-l dichloride ( I ) in JOO nil. of benzene a t 0'. T h e heterogeneous mixture was itirrcd a t room temperature for 24 hr. The solid recovered b y filtration was washed with benzene, ethanol and water. T h e dried crude product was crystallized from hot chloroforrn-ethanol; j-ield 13.4 g . (76%), 1n.p. 2c55-25Go.
[TI,
( I ( i ) I . J . Heilweil and Q. Van U h k l e , J . P h ~ s .Chenz., 69, 9 4 1 (L',l-)dl, (17) 1'. 1. l l o r y , "Principles of Polymer Chemistry," Cornell Univ c i i i t y Press, ltliacn, S . Y., 10.i3, pp. 291-303.
[ C O N T R I R U T I U V F R O M THE D E P A R T M S N T O F
/lmzl. C:ilcd. for C?41€70SLO!~: C , 5(\.25; 1-1, 7.0:;; S , 5.17. Found. C , 56.26; H, i.20; S,?1.,'37. 2 . 1,l'-(Galactaroy1)-dipiperidine (V11 ;.~~~l)eacet!.latir)~i of VI by stirring 12.9 g . overnight at room teinperaturc with 200 ml. of 0.6 .V sodium methoside in inethanol afforded :t yellow solid t h a t was recovered by filtrxtion. After washing the solid with mctlianol, a suspension in riietlianol W;IJ neutralized by t h e :iddit.ioii of 2 V : iiydroc!lioric acid. T h e insoluble inaterial WJS recovered by filtration and washed with water. Pure l,l'-(gal:wtaro>-l)-dipiperidine was obtained on crystallization from hot r\',9-tlii1iethylfortnamide; yield 2.5 g. (295;), n1.p. 238-239' dec. .2tzal. Calcd. for C1611isS20~: C , 52.31; 13, 5.14; 9, 8.11. Found: C, 25.66; H, 8.39; K, 5.31. 3. Tetra-0-acetylgalactaric Bis-(phenylhydrazide) (VIII) . -Phenr-lliydrazine (38.0 nil., 386 mmol. was added slowly t o a stirred suspension of 29.0 g. (70 nimol.) of tetra-0galactaroyl dichloride (1, in 550 inl. of benzene a t 0". Thc. mixture was stirred overnight a t room temperature and thc solid xas filtered, washed with benzene, ethanol, dilutc aqueous alkali and water. The crude product as extracted with boiling acetone. T h e insoluble tetra-0-acetylgalnctaroyl bis-(phen!.lhydrazide) (VIII) was crystallized twice from ru',ru'-dimethylformaniide solution by adding ethanol and cooling; 5-ield 16.6 g. (42%), m.p. 257-258'. A n d . Calcd. for C?6H30N401~: C , c53.91; 13, 5.37; s, 10.03. Found: C, 53.99; H, 3.55, E,9.85. 4 . Galactaric Bis-(phenylhydrazide) (IX).--Dc:tcetyl;Ltion of VIII,7.1 g . , was accomplished by stirring with 140 nil. of 0.6 1%' sodium methovide in metlianol for 24 lir. Ltt room teinperaturr. T h e heterogeneous reaction inixturc: was filtered. Tlie solid, suspended in methanol, W,IS treated with 9 S hydrochloric acid until neutral, filtered, washed with inet!ianol and water, and twice recrystallizeti froin hot N.N-diniethrlformatiiide-ncetone t o eive nure
5 . Bis-( 2-hydroxyethyl) Tetra-0-acetylgalactarate. During the course of an unsuccessful attempt t o prepare a polyester !I? the condensation of tetra-0-acet-Igal dichloride Ti-ith ethylene gl>-colii sinal1 amount of cr material was isidateti. Thus, I , 11.9 g., WLS dissolved ill 60 rnl. of ethylene glycol with heating. T h e solution was concentrated a t 2 mni. pressure and 14.?--1.j.?'. hlethanol vias added t o the resulting sirup and tlic Tvliite solid which formed was sep:ir,ited ;ind mashed with iiiethanol and water. Crystallization from :icetone afforded l)ij-!.'-h?.rlro.;~etli~l~ tetra-0-acetylg.ilact;ir;lte; yield 80 tiig., n1.p. 209". .4n(il. Cxicci. fur c1sTr~60,:: C 46.4.'; TI, 5.57; inol. w t . , 468. Found: C, 46.47; 11, 5.23; rnol. wt., 457 (Rast).
Ackiiow1edgment.--Lye appreciate the cooperation of Dr. Quentin \'an Winkle in carrying out the light scattering molecular weight studies. CC)LUMLIUS 10, O ! i I o
CHEXISrRY -ANI)
C I I E M I C A L ~ . X G I N E E R I S G ,S T A N F O R D L ' N I I ' E K S I I ' Y ]
Sabinene Hydrate: a Constituent of American Peppermint Oil] 13Y J O H N
11'. DALY,F.CHARLOTTE GREEN
AND l-ere maintained a t 80". Aliquots of 10 11. vxre renio\-ed a t 0, 2, 4, 8 and 20 hours. These aliquots were :irialyzed on a 12-foot Carbowax-coated vapor phase chroriiatography column maintained a t 130". The area of t h e pcak resulting from the alcohol was divided by the total :irc:L o f ;ill the chromatogram peaks t o give the approximate pwcentage of the alcohr~l. Tlic. results are given in Table T. STANFORD, C A L I F .
FATTY ACID PRODCCERS' COIJNCILOF THE ASSOCIATION OF AIIZERICAS SOAPAND GLYCERIXE PRODUCERS, INC., AND THE EASTERXREGIONAL RESEARCH LABORATORY1]
THE
V.2 Vinyl a-Diethylphosphonates
Phosphorus Derivatives of Fatty Acids. BY
RICHARD s A S I N , 3
ROSEl f A R I E N A U M A ~AND Y ~ DANIELSWERX RECEIIED
JULY
7,19.58
Vinyl or-bromo esters have heen prepared in 30-60% yield from vinyl acetate and the appropriate CZto C18 straight chain or-bromocarboxylic acid (equntion 1). By heating the vinyl a-bromo esters with triethyl phosphite, the corresponding vinyl a-diethylphosphonates were prepared in 35-75570 yield (equation 2). T h e vinyl a-phosphonates are colorless, odorless liquids which are insoluble in water and soluble in organic solvents Under prolonged heating with benzoyl peroxide, they form polymers v i t h a low degree of polymerization
The first three papers in this ~ e r i e s , ~described -~ the preparation and properties of dialkyl acylphosphonates, dialkyl acyloxyethyl phosphonates and trialkyl a-phosphonates, respectively. The present investigation deals with the synthesis and properties of some new vinyl esters of a-diethylphosphonocarboxylic acids. The literature describes numerous examples of unsaturated esters of phosphonic a~ids.~-lOThese compounds have the general formulas 0
0
t
f
R P ( O C H ~ C € € = C I I ~ )or 2 RCH-CHP(OCH?CH=CH:)?
In contrast to alkenyl phosphonates, the literature reports relatively few examples of alkenyl phosphonocarboxylates. The examples appear to be limited to the vinyl (I) and allyl (11) phosphonoI n these compounds, the alkenyl group of the ester is attached to carbon and not to phosphorus as in the previous types. (1) Eastern Gtilization Research and Development Divisiun, Agricultural Research Service, U . S . Department of Agriculture. Article nut copyrighted. ( 2 ) Presented a t tne liall IIeeting of the American Chemical Society, Chicax", IlI., September 7-12, 1658. Faper I T in this series, I n d . Eng. Chem., d a t a series (195X). (3) Fellow of t h e F a t t y Acid Producers' Council of the Association of American Soap a n d Glycerine Producers, Inc. Jnrdan, C. R. Eddy and n. Swern, THIS Jordan a n d I). St%eet.n,z b i ~ l ,78, , 6023 f1956). (6) R . .Ickernian, I t . A ? . Chlddek and Jj. Slrern, ibic!., 79, fj.524 (1957). ( 7 ) 1%.IT Coover and T. H. rlickei, U. S . P a t e n t 2,li3ij,027 (19331. (8) I
