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COMIRIUNICATIONS T O THE
43(wc yield from in-trifluoromethyl~~hetiol and w-bromoundecylic acid. T h e compound boiled a t 195-199" a t 1 m m . and when recrystallized from Skellysolve B it melted a t 42-43". A n d . Calcd. for neutral equivalent: 346. Found: 351. Benzilidene-9,lO-dihydroxystearic Acid.-Dry hydrogen chloride was passed into a solution of 24 g. (0.076 mole) of 9,10-dihydroxystearic acid and 9 g . (0.084 mole) of bmzaldehyde in 300 cc. of dry benzene. The solution was refluxed and the water removed as formed. On distillation there was obtained 21 g. ( 6 8 q ) of product boiling a t 240' ;tt 0.1 mtn. .4naZ. Calcd. for C?jHd~O,: C, 74.2; H, 9.9; neut. equiv., 405. Found: C , 74.0; €1, 1O.l'); neut. equiv., 401. o-Chlorobenzilidene-9,lO-dihydroxystearic Acid. ---This compound was prepared by the same procedure as above. From 7R g. (0.24 mole) of R,1O-dihydroxystearic acid and :Iri g. (0.25 mole) of o-ehlorobenzaldehyde there I W S ob-
EDITOR
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tained 63.7 g. ( 6 2 7 ) of product hoiling a t 2 4 5 2 5 0 i t 0.1 mm. Anal. Calcd. for C?sH30C10~:C, 63.4; FI, 8.9; CI, 8.1. Found: C, 68.8; H , 9.1; C1, 7.7. Dilauryl Mercaptal of 4-Aldehydophenoxyacetic Acid .Dry hydrogen chloride was passed into a >elution of 22 g . (0.12 mole) of 4-aldehydophenoxacetic acid and 50 g. (0.25 mole) of lauryl mercaptan in 250 cc. of dioxane. T h e solution was refluxed for one hour a n d then poured into ice water. The crystals were collected and after recrystallization from alcohol melted at 7i)-74'; yield, 41 g. ( X c ; ) . 4 n analytical sample recrystallized from Skellysolve B melted a t 71-75". A ~ t n l . Calcd. for C:q:jH;,O&: C, (i9.8; H, 10.3; neut. equiv., 566. Found: C , W.7; IT, 10.6;; iieut. cquiv., .5W. CHEMISTRY LABORATORY THEOHIOSTATE ~NIVERSITI. h R E N C E RAPOPOR'I COIJWBKJS 1 0 , OHIO b f E L V I S s. S E I Y M A S RECEIVEDOCTOBER7 , 194ii
A NEW SYNTHETIC METHOD FOR MANY-MEMBERED CARBON RINGS
cc. of the ether was distilled. The remaining ether was separated from the precipitated amine salt Sir: by washing with water. X small amount of solid The recently described method for obtaining material (probably polymeric compounds) proved ketene dimers' made it seem likely t h a t under to be insoluble in both ether and water. The conditions of high dilution an appropriate bi- ether solution was washed once with 3 N hydrofunctional ketene should undergo self-condensa- chloric acid and twice with water. After drying tion to form' macrocyclic diketenes readily con- over magnesium sulfate, the ether was distilled, vertible to many-membered carbocyclic ketones. leaving a light yellow, mobile oil. To a solution of the oil in 10 cc. of absolute ethanol was added 3 Thus, a b.functiona1 ketene such as O=C=CH(CH2~,l---CH=C=0 should afford, after dimeri- g. (0.0.3 mole) of potassium hydroxide dissolved zation followed by hydration and decarboxylation, in 30 cc. of WZ, ethanol. .lfter refluxing on the steam-bath for three hours, the clear solution was cyclic ketones of the type acidified to litmus with dilute hydrochloric acid. r---i /co\ To this was added 130 cc. of water and 100 cc. (CHs),+? CO and (CH2),+2 (CH*),,+?,etc. was then distilled in order to remove alcohol and L - - J ------co/ any cyclononanone present. The distillate had a The usefulness of this method has been tested very pleasant odor, but attempts to isolate cyemploying sebacyl chloride' as the starting ma- clononanone as the semicarbazone were unsuccessterial for the preparation of a bifunctional ketene ful. The residue from the steam distillation was of the type described above. From a considera- made basi? to phenolphthalein with 10% sodium tion of t h e relative ease of forming many-mem- carbonate and extracted with ether. Distillation bered carbon rings,2 this ketene ( n = 6 ) should of the dried ether layer left a small amount of cyclize to yield ultimately cyclobctadecane-1 ,IO- pale yellow liquid, which crystallized into beautiful, large crystals on standing. Vacuum distilladione as the principal product. To a stirred, refluxing mixture of '7.2 g. (0.071 tion gave 430 mg. (1674) of crude crystalline cymole) of triethylamine, 0.4 g. of triethylamine clooctadecane-1, 1 0-dioce, collected from 1335hydrochloride and 500 cc. of absolute ether was 214' (0.4 mm.). The light yellow crystalline prodadded during thirty-eight hours 4.403 .g. (0.0184 uct was used directly in the preparation of the mole) of sebacyl chloride in 200 cc. of absolute disemicarbazone (m.p. 223-22'7" dec. (cor.)) and ether. Stirring and refluxing were continued for the dioxime (m.p. 1B3-16So (cor.)). -1sample of four and one-half hours more. Then, after stand- diketone after sublimation melted a t 95-96' ing at room temperature overnight, all but 230 COT.).^ ( 1 ) Hanford a n d Sauer, "Organic Reactions," Vol. 111, pp. 108140 (1946). This excellent chapter presents a complete literature survey of the preparation of ketenes and ketene dimers. (2) I( Ziegler and R. hurnhammer, A w n . , 613,43-64 (1934).
(3) L. Ruzicka, et d., Hclu. Chijn. A c ~ Q11, , 506 (1928). These workers report cyclooctadecane-1,lO-dione (m. 11. 96-97'); disemicarhazone ( m . 11. above 230' dec ) ; a n d di(rxime (m. p. I ( i 6 1680).
COMMUNICATIONS TO THE EDITOR
Feb., 1047
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.l complete study of the applicability of the synthetic method outlined above is in progress.
there was obtained by acetone elution and crystallization from ethanol, a substance crystallizing in tufts of fine needles; m. p. 134-13Ao, mixed T H E BAKERLABORATORY O F CHEMISTRY CORNELL UNIVERSITY A . T. BLOMQUIST melting point with 6-a-D-glucopyranosido-/?-DSEW YVRK ITHACA, R. D. SPEXER glucose octaacetate 120-125', [ N ] * ~ D 86' (c RECEIVED JANUARY 20, 1947 1 .6, chloroform). This material is the hendecaacetate of a trisaccharide and its structure is under further investigation. T H E CRYSTALLINE OCTAACETATE OF Anal. Calcd. for C ~ ~ H ~ I O I ~ ( C H : C, ~ 49.69; CO)~~ 6-CY-D-GLUCOPYRANOSIDO-P-D-GLUCOSE H, 3.63; mol. wt., 966.8. Found: C, 49.46; H, - -Sir: 331 ; mol. wt. (Rast), 971. The polysaccharide dextran ( [ a I 2 O ~ lS0O; OF CHEMISTRY DEPARTMENT L. LV. GEORGES c I , water) produced by Leuconostoc dextranicum THE OHIOSTATEVTNIVERSITY I. L. MILLER was hydrolyzed a t room temperature in %yo solu- COLUMBVS, OHIO M. L. U'OLFROM tion in 30yo hydrochloric acid to approximately RECEIVED J A X U A R17, Y 1917 two-thirds completion ( [ a ] " " D of solution 10.7'). -After removal of inorganic ions by successive treatment with lead carbonate, hydrogen sulfide, T H E ANTIBACTERIAL ACTIVITY OF +AMINOBENZENEPHOSPHONOUS ACID sodium bicarbonate and -1mberlite resins (IR-100 anti TR-J), the D-glucose was removed by yeast Sir : fermentation and the sirup obtained on solvent It has been shown by Kuhn, AIoller and Wendt' removal was acetylated with hot acetic anhydride that phosphanilic acid (P-H&JC6HaPO(OH)z) has and sociium acetate. The resultant mixture of a slight antibacterial action, similar in nature to sugar acetates was chromatographed' on Magne- that of the sulfonamides in being antagonized by solLCelite employing benzene-ethanol develop- p-aminobenzoic acid. Proceeding on the assumpment under such conditions that any monosac- tion that the strength of the sulfonamide-enzyme charide prescnt would be removed from the col- complex is increased with decreasing acidity,? we umn. The material from the lowest zone was have prepared p-aminobenzenephosphonous acid, rechromatographed in similar fashion and the p-H?NCaHIP(OH)2,by the procedure lowest zone material again obtained was crystalAlC1, H>O lized (elongated prisms) from ethanol; m. p , ChH,Br + PCl? p-BrCeHJ'C12 14:3-144", [ a ] % ) 97' (c 2 . 7 , chloroform). p-BrCeHAP(OH), (1) Anal. Calcd. for C12H14011(CH3CO!S: C, cui0 4!i,.X; H, 5.63; CHJCO, 11.79 cc. of 0.1 S so- p-BrCaHZ(OH I 2 SHlOH ~-H&CSH~P(OH)~ dium hydroxide per 100 nig.; mol. wt., (iiS.($. (2) Found: C, 49.74; H, 5.(ji; CHJCO, 11 The first step, the preparation of p-bromobenzenemol. wt. (Kast), 6SO. Since methylation ~ t u d i e shave ? ~ ~ demonstrated phosphonous acid, has been carried out previ~ second step, the synthesis of the that the polysaccharide employed in this wdrk is o ~ s l y . The built up of a-D-glucopyranose units linked in the amino compound, is similar to that used by 1,&position, it follows that the disaccharide iso- Bauer4 to prepare phosphanilic acid. lated must be (i-a-D-glucopyranosido-8-D-glucose The product obtained has these properties. octaacetate. Its determined rotation is in agree- m.p. 169'; eqilivalent weight, calculated 157.1, ment with the value predictable by application of found 158.0; analysis, calculated P 19.TIC&,found thc, isomtation rules of Hudson. The same acet- P 19.6674; solubility in water a t 0' about .jq; ylation and chromatographic procedure was ap- ph-,3.6s. The activity of p-arrinoben7enephosphonous plied to the sirup soluble in SO' ethanol that was ?.btained essentially according to the procedure of acid was tested against E coli arid found to be Ortenblad and liyrbackf from the enzymic hy- slightly less than that of sulfanilamide. This tlrolyzate o f amylopectin (waxy maize) after re- antibacterial action was antagonized by p-aniinonova1 of most of the maltose and D-glUCoSe by benzoic acid a t concentrations approvimately yeast fermentation. I n this case the lowest zone equal to those necessary to counteract sulfanllun the chromatogam was composed of @-maltose amide. Further tests on this substance and reoctaacctate (m.p. 1.Y-160°, mixed rntlting point lated compounds are in progress. OF CHEMISTRY l Z I - l f i O O un!.hangcd; [a]"D W 0 ,c 1.1, chloro- DEPARTMEYT I M KLOTZ zone immediately above this NORIHIYESTERN UKIVERSITY
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