Aug. 20, 1959
w-DIALKYL PHOSPHONOUNDECXNOATES
of the residual oil gave 1 I S 7 (fiii.070) of 10-cvanndecvl thiocyanate. X pulifitA product (b.p. 180-1G2.5" (0.OY mm.), diu, 0.982, n2% 1.4806) was obtained by redistilldtion. Calcd. for c , ~ H ~ ~ N ~ s :64.25; H , 8.99; N, 12.49; S , 14.29. Found: C, 64.26; H , 9.32; N , 12.58; S, 14.08.
c,
3-Cyanopropyl thiocyanate, b.p. 112.5-116° (0.06 rnm.), dZo41.100. n Z 51.4968. ~ was DreDared in 76.5% yield from 4hr&nobutyronitrile. ~~
4335
A n d . Calcd. for C5HsNrS. C, 47.50; H , 4 79; N, 22.21, S, 25.41. P o u l ~ l : C, 47.r17; 11, 4.80; N, 22.61; S, 25.30. 4-Cvanobutvl thiocyanate, b.D. 131-132° (0.1 mrn.), d20, 1.098, n*bD i.492i, was prepared from 5-bromovaleroin 72*8%Yield. Anal. Calcd. for CeHsN2S: C, 51.40; H , 5.75; N, 19.98; S, 22.87. Found: C, 51.74; H, 5.93; N, 17.51; 22'50* VILLE LA SALLE, QUEBEC
CONTRIBUTION FROM T H E FATTY ACID PRODUCERS' COUNCfL O F THE ASSOCIATION O F AMERICAN SOAP AND PRODUCERS, INC.,AND T H E EASTERN REGIONAL RESEARCH LABORATORY']
GLYCERINE
Phosphorus Derivatives of Fatty Acids. VI.2 w-Dialkyl Phosphonoundecanoates BY
RICHARD SASIN,3 ROSEMARIENAUMAN3 AND DANIEL SWERN RECEIVED FEBRUARY 16, 1959
A series of o-bromoundecanoates has been prepared in 5 5 9 6 % yield from w-bromoundecanoic acid and alcohols or phenol: Br(CHz).&!OOH ROH + Br(CHz)loCOOR HaO where R = CHI, C2H6, n-CaHo, n-CsHts, 2-ethylhexyl, n-C1&6, CeHa. By heating the o-bromoundecanoates with trialkyl phosphites, the corresponding w-dialkyl phosphonoundecanoates were prepared in 53-87s yield: Br(CH,)l&OOR (R'O)3P + 0 P(OR')z(CHz)&OOR -I-R'Br. Trialkyl w-phosphonoundecanoates prepared include: R = R' = CHs, C&, n-C4H9, n-CeHl3, 2-ethylhexyl, n-C12H26. Mixed w-dialkyl phosphonoundecanoates prepared include: R = C2H5, R' = n-C4H9; R = 2-ethylhexyl, R' = n-C4Hp; R = C~zHzs,R ' = n-C4Ho; R = C&, R ' = n-C,Ho; R = n-C4H9; R' = 2-ethylhexyl; R = 2-ethylhexyl, R ' = C2Hs; R = GH6, R' = 2-ethylhexyl. The compounds in which R = 2-ethylhexyl and R' = and R = CaH6 and R' = 2-ethylhexyl were prepared by another synthetic method. The w-dialkyl phosphonoundecanoates are colorless, odorless, thermally stable liquids, insoluble in water and soluble in organic solvents.
+
+ +
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0 0 OR 0 I n this Laboratory, recent research on the prepaIt II II ration of pure derivatives from fats has been RO-C-( CHz),-C-OR 0 t I&CHZ)IO--C-OR directed mainly toward the correlation of structure I with important physical properties desired in OR plasticizers and also in synthetic lubricants. I1 I Groups containing the phosphorus atom, for exn = 4, 7, 8 ample, are known to impart useful properties to plasticizers, and a number of phosphorus-containThis paper also describes the preparation and ing plasticizers are commercially available. properties of a series of w-bromoundecanoates, For the past four years we have been systemat- used as intermediates in the preparation of 11. ically preparing long-chain phosphorus compounds They were prepared from w-bromoundecanoic acid of various types. These are trialkyl p h o ~ p h a t e s , ~and alcohols or from the acid chloride and phenol. dialkyl acyloxyalkyl phosphate^,^ dialkyl acyloxy- The esters prepared include: methyl, ethyl, nalkylphosphonate~~ and alkyl (a-dialkylphosphono) - butyl, n-hexyl, 2-ethylhexyl, n-dodecyl and phenyl. a1kanoates .e All of these compounds are colorless liquids a t Since most low temperature plasticizers are room temperature, insoluble in water and soluble dialkyl esters (I) of dicarboxylic acids, such as in organic solvents. The physical properties, adipates, azelates and sebacates, i t was decided to yields obtained and analyses of the w-bromoprepare a series of compounds similar to these di- undecanoates are summarized in Table I. basic esters but containing a dialkylphosphono By heating the w-bromoundecanoates with a group in place of one carboxylic ester group. The 1 0 0 ~molar o excess of trialkyl phosphite a t elevated w-dialkyl phosphonoundecanoates (11) are such a temperature for several hours, the w-dialkyl phosseries of compounds; their preparation is described phonoundecanoates were prepared in 53-8770 here. No reports on the preparation and study of yield. After the unused trialkyl phosphite was the physical and chemical properties of the w-dialkyl removed, the residue was distilled under diminished phosphonoundecanoates could be found in the litera- pressure. ture. The trialkyl w-phosphonoundecanoates prepared include: trimethyl, triethyl, tri-n-butyl, (1) Eastern Utilization Research and Development Division, Agritri-n-hexyl, tri-2-ethylhexyl and trilauryl. The cultural Research Service, U. S. Department of Agriculture. Article not copyrighted. mixed w-phosphonoundecanoates synthesized in(2) Paper V is in THISJOURNAL, 80, 6336 (1958). clude: ethyl w-di-n-butyl, 2-ethylhexyl w-di-n-butyl, (3) Fellow of the Fatty Acid Producers' Council of the Association of lauryl w-di-n-butyl, phenyl w-di-n-butyl, n-butyl American Soap and Glycerine Producers, Inc. w-di-2-ethylhexy1, 2-ethylhexyl w-diethyl and ethyl (4) D. Swern, W. E. Palm, B . Ackerman and L. P. Witnauer, Chem. b Eng. Data Series, S, 346 (1958). w-di-2-ethylhexyl. The last two compounds were JOURNAL, '78, (5) B. Ackerman, T. A. Jordan and D . Swern,THIS prepared from 2-ethylhexyl undecenoate and 6025 (1956). diethyl phosphonate, and ethyl undecenoate and (6) B. Ackerman, R. M. Chladek and D. Swern, i b i d . , 79, 6524 di-2-ethylhexyl phosphonate under free radical (1957).
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Vol. s1
IIICHARD SASIN, ROSEMARIENAUN.XN ."i~ DANIEL SWERN TABLE I 0 W - n R O ~ ~ I O l ' S I ) F . C A N O A T E S ,~ ~ . ( C I I ? ~ I , ( ! ~ ~ ?
Yield,
I
