2644 KENYON AND PICKARD : IN VESTIGA‘PIONS ON DEPENDENCECCX LVI I I .--hvestigat ions on the Dependelice oJ’Rotatory Power on Chemical Constitution, PartI X . 2 %, e Rot a tory Powers of 1 -.ATup h t h y 1 - n - h ex y 1 -carbinol and its E s t e mBy JOSEPH KENYON and ROBERT HOWSON PICKARD.THIRTY-EIGHT optically active carbinols of the formulaR,*CH(OH)*R,have been described so far in this series of investigations, and withone exception have been shown to possess certain characteristics asregards dispersive power. Thus their rotatory powers for light ofwave-length ranging from that of sodium yellow to that of mercuryviolet not only increase continuously with decreasing wave-length(that is, the compounds exhibit what is commonly spoken of asi~ormal dispersive power), but also conform t o the law of simpledispersion expressed by Drude’s equation with one term,a = k/ h2 - h,2 (compare Lowry, Pickard, and Kenyon, this vol.,p.94). Further, a dispersion ratio, such as, for example,H g g z , is in the cases of many of the carbinols approximatelyconstant over a range of temperature extending up t o their boilingpoints, and even in the others varies only to a very slight extent,whilst the dispersion ratio is only affected to a very slight extentby solvents. It is probable, however, that this is a special propertyof this class of compounds, the rotatory powers of which are notaffected to any large extent by increase of temperature or solution.Indeed, on reference 60 the ‘‘ characteristic diagrams ” (for example,see P a r t V., this vol., p.847) for a homologous series of suchcarbinols these properties appear as an obvious arithmetical fact,since the violet and green lines of the diagrams intersect so closeto the zero. It should, however, be borne in mind that the methodof plotting rotation data known as “ Characteristic diagrams ” asdeveloped by the present authors for the correlation of the rota-tion data of many compounds of allied structure-whilst provingextremely useful in several directions-is, however, largely empiri-cal, having been devised originally on theoretical grounds byArmstrong and Walker (Proc. Roy. SOC., 1913, [ A ] , 88, 388) t oaid in the explanation of the at~ornalous dispersion of a compoundby assuming the presence in i t of two dynamic isomerides ofdifferent optical properties.It also seems desirable to suggest that inferences drawn from\ ioleOF ROTATORY POWER ON CHEMICAL CONSTITUTIOK.2645variations in the magnitude of a dispersion ratio are likely to provemisleading, whilst the use of negative and positive signs for suchratios in the region of what is commonly known as anomalousdispersion has apparently no meaning whatever.Among the carbinols referred to above the conspicuous excep-tion is E-1-naphthylmethylcarbinol (Part VI., this vol., p. 1116).The rotations of this compound appear to obey the law of simpledispersion only a t temperatures above 160°, whilst in the super-cooled state Lhe carhinol exhibits the phenomenon known as anoma-lous dispersion a t and below a t’emperature of about loo.Soextraordinary, then, are the optical properties of this carbinol thatit seemed desirable to investigate some of its homologues, but owingt o the many experimental difficulties only d-1-naphthylqz-hexyl-carbinol has been prepared.The properties of the new carbinol are quite analogous t o thoseof the corresponding methyl compound. Thus in the homogeneousstate (see Fig. 1 and table I) the dispersion is “anomalous” (foryellow to violet light) a t temperatures between about 2 2 O and 38O,but the rotations conform t o the law of simple dispersion a t aboutand above a temperature of 180°. The regular character of therotation curves seems to negative any suggestion that the anoma-lous dispersion is due specially t o polymerisation in the neighbour-hood of the melting point of the carbinol, although they show thatthe cause of the “anomaly” is gradually removed by increase oftemperatare.The majority of chemists appear t o favour the explanation ofanomalous dispersion in compounds of simple constitution by theassumption of the presence in what is otherwise the homogeneouscompound of two dynamic isomerides differing in optical sign anddispersive power.It has been suggested already (Part VI., Zoc. c i t . )that in the case of these naphthylcarbinols such isomerides arecaused by a difference in the disposition of the valencies in thenaphthyl radicle. An alternative suggestion made by Patterson(T., 1913, 103, 145) that this phenomenon is due to a successionof maxima and minima on the rotatJon curves occurring a t differenttemperatures for light of various refrangibilities, whilst very diffi-cult of direct experimental test, is nevertheless rendered verydoubtful in the authors’ opinion by the accumulation of datarecorded in these investigations.It has now been shown that the presence’ in an optically activecompound of a naphthyl group attached a t the “a”-position orof an esterified carboxylic group is associated very frequently withthe phenomenon of anomalous dispersion.I n each case tempera-VOL. cv. 8 2646 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEture has a great effect on the phenomenon, increase of temperaturedestroying it in the case of naphthyl compounds, but bringing itto view in the case of the esters.It is desirable, however, that theterm " anomalous '' dispersion should no longer be used. PortionsFIG. 1.61-Naphthyl-L&)*-40'Temperature.0' 1of the rotation curves on either side of the region of rcanomalous"dispersion have dispersion ratios which rapidly increase or decrease." Anomalous " dispersioc as commonly understood refers as a rulemerely to portions of the rotation curves artificially selecte,d accord-ing to the wave-lengths of light under consideration. In view oOF ROTATORY POWER ON CHEMICAL CONSTITUTION. 2647Lowry’s work (T., 1913, 103, 1067 et seq.) it is much better touse only the terms simple and compJex as applied to dispersivepower according as the rotations conform to Drude’s equation withone or more terms.Among the large number of compounds studied in these investi-gations the 1-naphthylcarbinols a t low temperatures and the estersdescribed in the authors’ previous communications a t high tem-peratures tend, then, to exhibit compIex dispersive power, thedispersive power becoming simpEe in each case if the conditions oftemperature are reversed.These generalisations ++ are confirmed by the optical properties ofthe esters of the two naphthyl carbinols with normal fatty acids,since it has been found that the acetate of I-1-naphthylmethyl-carbinol and a homologous series of esters (ranging from the acetateto the n-undecoate) of d-1-naphthyl-n-hexylcarbinol each exhibitscomplex dispersive power a t all temperatures from 20° to 200°, thelimits of the experimental conditions.The dispersion ratios forthese esters are not affected much by temperature, and are nearlyidentical throughout the series. This is noteworthy, not onlyfor the exceptions, but also as occurring in a series all membersof which have complex dispersions. The dispersion ratios of eachester, however, are about 5 per cent. greater in carbon disulphidesolutions than in the homogeneous state.The configurations ascribed to I-1-naphthylmethylcarbinol andd-1-naphthyl-n-hexylcarbinol, although these compounds and someof their derivatives are under certain conditions dextro- and laevo-rotatory respctively, are justified by drawing the characteristicdiagram for each carbinol, when i t will be found that the twodiagrams form exact mirror images of one another.As has beenalready mentioned, such diagrams are based on the assumptionof the presence in the carbinols of two dynamic isomerides differingin optical sign and dispersive power, but in the case of the estersof these cai-binols there may be assumed to be present four dynamicisomerides in each ester. It is therefore not surprising that therotation data f o r the esters recorded in the experimental partcannot be correlated on the characteristic diagrams of the carbinols,although these four dynamic isomerides would in pairs have thesame optical sign.* The authors arc aware that many of the generalisations stated in this andprevious papers of the series are open to the criticism that the same are based onpolarimetric readings of small magnitude.However, they feel that the concordantresults which have now been obtained for a very large number of compoundcl justifytheir generalisntions.8 K 2648 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEThe trend of the values of the molecular rotatory powers of themembers of this series of esters is dissimilar to those of the otherFIG. 2.4 5 6 7 4 q I0 tiNumbel. of cnrbna atoms in m y 1 grot6p.series of wters described in these investigations. Thus it will beseen from Fig. 2 that the curves connecting molecular weight andmolecular rotatory power determined under several conditions oOF ROTATORY POWER ON CHEMICAL CONSTITUTION. 2649temperature and solution show maxima a t the propionate andoctoate in additlion to the maximum so commonly exhibited at theFIa.3.hexoate (or valerate). This somewhat irregular result is perhapsnot surprising in a series of esters of such complexity, that is, ascompared to the esters previously described, which have been thos2650 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEof carbinols of simple structure (compare, however, Part III., T.,1912, 101, 1430). To explain this is difficult, but it is significantthat the maxima a t the propionate and octoate follow one anothera t points ic the series in the interval between which the chain hasgrown by five carbon atoms, that is to say, a t the octoate thegrowing chain may be assumed to have all but returned on theposition occupied by it in the propionate.It is, however, possiblethat the mass of the growi12g chain as it approachea (or just exceeds)that of one of the other groups (for example, the hexyl or naphthylgroup) may have an additional effect on the molecular rotatorypower and cause Dome special exaltation.I n Fig. 3 the effect of temperature on the rotatory powers of theesters is illustrated. I n general this effect (within the experimentallimits) is a common one on a11 the members of the series, althoughthere is a significant change of slope in the curve for the octoate.Temper-ature.loo20406080100120140160180200D:.1.03101.02321.00750.99110-97540-96000.94440.92850.91290-89700.8813TABLE I.d-1 -Naph t hyl-n- he3[a]:.- 11.26"- 1.51 + 12-4623.2931-2237.5041.0342-7143.8244.1342.62ra1;l..- 14.89"- 2.05 + 13.8526.8937.4744-3748-7851-3452-8663.6751-06[aICi.- 40.25"- 12-75 + 16.9240.4158.9572-9582.5887.2689.8290.8686.26qlcarbinol.[MIL.- 27.24"- 3.66+30.1556-3575.5490.7499-28103.4106.0106.8103.0[MI:,.- 36.03"- 4.97 + 33.5265.0790.67107.4118.0124.3127.9129-9123.6Dis-persion[M']ti. H g g .- 97.40" 2.704-30.85 6.213 + 40.96 1e.22297.79 1.503142.7 1-573176.5 1.644199.8 1.692211.2 1.700217.4 1.699219.9 1.693208.6 1.68Temper-ature.20'40608010012014016018020020'406080100120140160180200Dtp.1.02621.01100.99470.97850.96240.94600.93000.91390.89790.88161.01471.00020.98500.96920.95210.93390.91500.89610.87780.8595[a]:. + 23-85'28.1532.1235.1037.7539.6441.2042.3543.1043.3428.59'33-9336.6539.6242-0743.8245-1746.2447-0847-75[a]: e*+25.05O29.6633-5036.8939.5141.7843.4444.4244.8244.8430.18'34.4338.1341.2843.9645.7347.2048.3549.1249-71TABLE 11.A ce tat e of d-I-Naph t h yl-n-hex yl car binol.[a];,.+ 28.68'34-0738.7342.4845-5048.0951.3951.8451.40* 50.0334.69'39.9444.3947.9250-7652.9154.7056.1957.0357.51[.]ti*+53*16'63.1671-5879.1884-7889.4193.0795.4597-1297.90CMIt + 67.74'80.0591.2299-68107.2112-6117.0120.2122.4123.1Propionat e.64.36'74.0383.0189.7695.5499-40102.7105-1107.0108.185- 17'98-11109.2118-0125.4130-6134.6137.8140.3142.3CMlZe.+71.15'83.9595.13104.7112.2118.7123.4126.2127.3127-489.93'102.6113.8123.0131-0136.2140.6144.1146.4148.Tempera-ture.20'40608000204016018020020"406080100120140160180200D:.1.00500.98990,97440.95870.94310.92730.91160.89570.88000.86430.99740.98160.96600.95000.93480.91910.90350.88740.87170.8559[.I;, + 27.02'30.7133.7136.0237.8739.1340.1741.0441-6642.01-+ 22-23"25.4228.1930.4732.1833-4734.4535-1 135.5135.69[a];, '+28*16"32.1535-4437.8639.7741-2242.2743.1143.7544.10+ 23-30'26.6529.5331-8433.6735.1036.0836-7337.1537.33[ a d .+ 32-54'37-1641.0044- 1146-1547-6948.8449.8250.4650.71+ 26-73'30.7134-0936.7438.8940.5241.7342.4842-9443.04TABLE I1 (continued).n-Butyrate.[a]:i*69.3476.6881-9386.2489.0291-4993.4294.5894-99+ 60.22' .[MI:. +- 84.29'96.83105.2112.4118.1122.1125-3128.0130.0131.6n-?lal erat e.+ 49.45"57.6864.3069.0072-6975.8878.1 179.5080.5281.08+ 72.47"83.8591-8999.31104.9109.1112.3114.5115-8116.3" 7 e . + 87-100-110.6118.1124-128.6131.9134-136.6137.6+ 75.95"86-96-103-109.7114.4117.6119.8121.2121.TABLE I1 (continued).n-H exoate.Temper-ature.20°40608010012014016018020'406080100120140160180D:.0.98940.98630.96960.94330.92720,91120-89550.88000.86430.98300-96740.95180.93600.92000.90420.88860.87250.8570[a];. + 21-12'23.7926-3527.9429.3430.3731.2732.0232.62+ 19.63'21.9724-1125-7426.8327.5028.0228.5429.05~a14.e + 22.36'25.1027.7629-533 1.0632-1633.0533.7634.46+ 20.59"23.3125.3126.8528.0328.8229.3929.9630.51n-Heptoat e.+23-68"26.4628.7730.5631.9633.0333-7634-3935-50[MI$.+71-81'80.8789.6094.9999.74103.2106.4108.8110.9+ 69.50'77.7583.3591.1494-9997.3499.19101.0102.TABLE I1 (continued).n-Octoa t e.Tempera-ture.20'40608010012014016018020"406080100120140160180u:.0.97970.96500.95050.93570.92100.90600.89130.87660.86170.97260.95760.94250,92760.91260.89770.88300.86780.8529bit.f-21-13'23.4425.2326.4427.3628.0528.4928-7528.89+ 19-06'21.2522.8023.8224-5725.1525.6025-8826.03[a]:,. + 22.1 1'24.6726.5727-9328-8529-4729.8830.1430.34+ 19.68'21-8223.4524.6125-4626.2226-7727-0527.14[alir.+ 25-46'28.3930.6132-1533.1933.9134.4434.8135.03+ 22.88'25.2227-1628.5229.5830.4230-9931.3431.48ial:i*53.2757.4460.4962-3863.5764.6365.6966.70$47.56' -[MIL.f 77.75"86.2692.8597.29100.7103.2104.8105.8106.3n-Nonoate.+ 72.85'81.1987.1091-0193.8596.0797.7798.8899-45[MI&. + 81.36"90.7697.77102.8106.2108.4110.0110.9111.6+75.19'83.3789.5894.0197.27100.2102.3103.3103.Temper-ature.20°40608010012014016020Q406080100120D: .0.96930-95400.93890.92370.90860.89370.87880.86350.96140.94680.93250.91790.90310.8885[alt,. + 17-13'18.8920.4521.6522.6623.1823.6924.08+ 16-44'18.1719.6320.6521-3521.78[a1 :-e.+ 18.09"19-8221.2522.4523-4224.0824.5825-04TABLE I1 (continued).n-Decoate.[41;r.+ 20.80"22.8824.5525.9227-0227-8628.4428.95n- Undecoa t e.+ 17.08' + 19-76'18.79 21-9720.24 23.2821.29 24.2222.04 25.0222.48 25.55[MI:.t-67.82"74.8180.9885.7489.3591-8193.8295.39+ 67-39'744780.4884.6587.6489.3Temper-ture.20"406080100120140160180D:.1.10441.08981,07331.06521.03681.01851.00020.98200.9635[a]:.- 32-28'39.5144.5849- 1852.8555-2256.7858.1159-29TABLE 111.A ce tn t e of 1-1 -~TapIi t hylrne thylcarbinol.[aIL IaIfi. [MIX.- 38.90" - 73.79" - 69.07'47.47 88-02 84.5554.04 101.51 95.4359.39 113.02 105.264.21 121.57 113.167-07 126.02 118.168.68 129.82 121-570.33 132.62 124.471.83 135.39 126.OF ROTATORY POWER ON CHEMICAL CONSTITUTION.2657EXPERIMENTAL.dl-1-Naph t h y I-n- h ex yl curb inol,C,,H,*CH(O~)*CH,*CH,*CH,=CH2~CH,~CH,.The reaction between magnesium 1-naphthyl bromide, and mhept-aldehyde proceeds smoothly only under certain conditions. Thenaphthyl bromide should be' free from the dibromide commonlypresent in the commercial product, and the aldehyde should befreshly distilled. The aldehyde, dissolved in ten times its volumeof ether, should be added very slowly to an excess of a diluteethereal solutiozl of the bromide, which is a t the time reactingwith slightly less than the calculated amount of magnesium, thetemperaturd of the whole being kept a t that of a mixture of iceand salt. The products of the reaction should be poured on to amixture of ice and dilute sulphuric acid as soon as the additionof the aldehyde solution is complete, and then immediately extractedwith ether.Much naphthalene being formed in the reaction i t ispreferable to remove it along with the ether and unchangedaldehyde by distillation in a current of steam. The residue isagain dissolved in ether, carefully dried, and fractionally distilledunder a pressure of 3 mm. All the carbinol is in the portionboiling above 160°, whilst the lower fractions contain the corre-sponding unsaturated hydrocarbon and the unchanged naphthylbromide. I n one series of operations, working with 620 grams ofthe bromide and 228 grams of n-heptaldehyde, the yield of carbinolwas 370 grams.dl-l-i\7aphthyZ-n-?~ezylcarbilzol boils a t 184O/ 4 mm., and on keep-ing sets t o a crystalline mass, which crystanises from light petroleumin feathery needles melting a t 41-42O.When guarded from theaccidental access of crystal nuclei, i t will remain for some time inthe supercooled condition, but solidifies rapidly when seeded.!rhe hydrogerh pht ?/alate, prepared by the method described inPart IV. (7oc. cit., p. ll26), is only sparingly soluble in lightpetroleuin, and is best crystallised from a mixture of this andbenzene, from which it separates in slender needles melting a t0.2245 neutralised 0.0226 NaOH. M.W. = 397. Calc. M.W. = 390.102-104° :Resolution of Hydrogen Yhthalate.The fractional crystallisation from acetone of the brucine saltsof the (d+ 1) phthalic ester yields readily the salt of the d-ester,ths process being carried out in t,he manner previously describedin detail (see inter &a, T., 1912, 101, 634).The ester (514 grams2658 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEwas dissolved in warm acetone (18 litres), digested with brucine(614 grams), and set aside to cry&allise. The first crop weighed300 grams, and was then recrystallised six times. The seventhcrop weighed 160 grams, and was the pure EBdA salt, which meltsand decomposes a t 124-125O. Two successive series of operationswith the mother liquors comprising respectively eight and ninecrystallisations yielded further lots of the salt amounting to 54 and15 grams respectively. Samples of the salt from the fifth andseventh crops of the first series of crystallisations and from thefinal cIops of the second and third series yielded hydrogen phthal-ates which had respectively [a], - 23*01°, - 22.469 - 22'42O, and- 22'62O respectively in (approximately) 5 per cent.ethyl-alcoholicsolution.ci-l-Nuphthyl-n-hexylcarbinol boils a t 1 7 8 O / 3 mm., solidifies instellate nodules, and melts a t 41.5O.The corresponding d-hydrogen phthalate solidifies in crystallinenodules, melts a t 9l0, and is soluble in all the common organicmedia. The crystalline sodium salt, which was obtained by theneutralisation of a solution of the ester in methyl alcohol withsodium methoxide and subsequent removal of the solvent in a desic-cator, is decomposed by water.Normal Esters of the Carbino1.-Of the esters prepared (seetable IV) the acetate, propionate, and n-butyrate were obtained bythe interaction of the carbinol and the respective anhydrides, whilstthe others were prepared by the action of the respective acidchlorides on solutions of the carbinol in pyridine.They are allviscous liquids a t the ordinary temperature, and have no odour, butthe higher members of the series often develop a faint yellowbloom, which is difficult to remove by redistillation, thus render-ing uncertain any polarimetric readings in the green, and par-ticularly in the violet portions of the spectrum.TABLE IV.Esters of d-l-Napkthyl-n-hexylcarbinol.Acetate . . . . . . . . .Propionate . . .n-Butyrate ...n-Valerate . . .n-Hexoate .. .n-Heptoate . . .n-Octoate . . . . . .n-Nonoate.. . , . .n-Decoate . . .n-Undecoate . . .€3. P167'12.5169'12184'13187'12.5198'12.5207"/3214'13222'14224Oj2-5232'/2.5D:O.1-02621.01471.00500.99740.98940.98300.97970.97260.96930-96142. (n- 1)ld.M.1.6471 151.3 .1.6403 158.71-5365 166.61.5332 174.31-5289 181.81.5271 189.81.5249 197.11.5225 205-21.5208 213.01.5188 221.028.5927.0222-2321-1219-6321.1319.0617-1316.44+ 67.74'85.1784.2972-4771.8169.5077-7572-8567-8267.3Solvent.Benzene . . . . . . . . . . . .Acetone .... . .. . . . . . .Ethyl alcohol . . . .Chloroform . . . . . . .Carbondisulphide . . . . . .Ethylenedibromide . . .. . .P yridine . . . . . . . . . . . .Carbondisulphide . . . . . .Acetic acid .........Chloroform . . . . . . .Benzene . . . . . . . . . . , .Pyridine . . . . . . . . . . . .Ethyl alcohol . . .Ethyl alcohol.. . . . .Ethyl alcohol ... .cm221022222210202222222222222222TABLE V.d-1-Naph t hyl-n-h exylcarb inol.Length Weightof tube, of solute. ingrams. a=. agr- Chi. [.ID* [Q]p [a]1.05890.68871.06661,09520.96860.92191.03401.01060.99001,18461.09171.04541.03261.05951.0826+ 8-70' + 10.48O + 18.25" + 74-67' + 89.97" + 156.7'2-39 2.86 5-20 71.48 85.54 155.57-69 9-39 16.52 65.37 80.02 140.87.80 9.40 16.41 64-76 78.03 136.26-41 7.73 13.30 60.15 72.52 124.82.51 2-96 5-30 54.46 64.00 115.04.38 5.23 9-02 42-36 50.58Hydrogen Phthalate.8.37 10.09 18.90 75.26 90.72 170.02.75 3.23 5.22 25.25 29.662.28 2.71 4.22 17-50 20.800.60 0.57 0.12 5.00 4.74-0.15 -0.36 -1.28 -1.30 -3.13 -11.14-2.55 -3.25 -6.93 -22.46 -28.63 -61.02Sodium Salt of the Hydrogen Phthalate.Rrucine Salt of the Hydrogen Phthalate.+3*50 $4.14 f7.37 +29*35 +35*52 +63*-1.45 -2.07 -5.62 -12.81 -17.39 -47.21All solutions for the determinations of rotatory power recorded in this paper were preparedt o 20 C.O.with the solvent a t the tcmperature of the laboratory, a t which temperatdre all observationTABLE VI.DetermitLatioiL of the Rotatory I-loicers of the Esters in (approa.) 5Ester.Acetate . . . . . . . . . . . .Propionate . . . . . . . . .Butyrate .. . . . . . . . . . .Valerate . . . . . . . . . . . .Hexoate.. . . . . . . . . . . . . .Heptoate . . . . . . . . . . . .Octoate . . . . . . . . . . . .Nonoate . . . . . . . . . . . .Decoate. . . . . . . . . . . . . . .Undecoate . . . . . . . . .Length Weightof of solutetube,cm.20202220202020202220ingrams.1.13630.95031.10191.13920.97680.98870.90201.15891.00011.1233(ID. aye. ugr. a,i. [alp + + + + + 3-84" 4.02" 4.64' 8.62' 33-80'3.45 3.60 4.17 7.65 36.313.90 4.08 4.70 8.70 32.183.10 3.34 3.76 7.04 27.212.59 2.67 3.05 5-85 26.522.30 2.44 2.76 5-10 23.262-28 2-37 2.72 5-12 25.272-55 2.65 3.05 5.74 22.012.15 2.27 2.53 - 19.542-02 2.12 2.41 4.80 17.99[a],,. + 35.38'37.8833.6629-3227-3324-6826-2722.8720.6418.88r Qlzr.+ 40.84'43.8838.7733-0131.2327-9130.1626.3223-0021.4c0Pd c TABLE VII.Determination of the Rotatory Powers of the Esters in (approx.) 5 perLengthEster.Acetate . . . . . . . . . . . .Propionate ...... . ..Butyrate . . . . . . . . . . . .Valerat e . . . . . . . . . . . .Hexoate . . . . . . . . . . . .Heptoate . . . . . . . . . . . .Octoate , . . . . . . . . . . .Nonoate . . . . . . . . . . . .Decoate.. . . . . . . . . . . . . .. . . . . . . . . EUndecoat eFoftube,cm.22202020101010102022Weightof Isolutein grams. a,. aye. agr. a s r i . [a]o. + + + + + 1.1254 13.80" 14.51" 16.95" 33-19' 111-5"1.0157 12.48 13.12 15.31 29.83 122.81.0665 12.05 12.74 14.84 29.12 113.10.9541 9.79 10.32 12.07 23.58 102.70.9485 4.70 4.87 5.68 11.40 99.101.2190 5.47 5.79 6.72 13.25 89-741.0342 4.48 4-71 5.49 10.75 86.641.0209 4.29 4.52 5.34 10.40 84-061.0773 8-44 8.87 10.36 21.50 78.361.0180 8.31 8.74 10.19 20.50 74.22[alw + 117.3"129.1119.5108.1102.794.9991.0788-5482.3578.05[a]<,.137.0" +150.7139.3126.6119.8110.3106.2104.696.2090.92662 KEXYON -1NDIPICK.lE D 1 KVESTIGATIONS ON DEPENDENCEDeterminations of Density (I):) ond Rotalory Power (aloe mm.) ofthe G'crrbinol am? ES~PTS i 1 ~ t h e Ilomogerteous S t a t e .The procedure in the determinations of rotatory power anddensity was the same as described in Part VITI .(this vol., p .2270) .d-l .NapF, thyl-n-?A exylccrrb ino? .Temp ................ 31" 63" 91" 146"D, .................. 1.0147 0.9890 0.9668 0.9234Temp . 15" 24" 26.5" 28" 36" 38" 42.5" 44" 49"a, ...- 6.04" +3*26 3.88" 4.30" 10.12" 11.40" 13-60" 14-94" 17.50"53" 58" 64" 76" 98" 104" 119" 145" 169" 194" + 20.00" 22.00" 25.14' 29.10" 35-72' 36.52" 38.80" 39-60' 40.10" 38.20"Temp . 15" 24' 25" 26.5" 28" 32.5" 39" 43"a g l . ..... -8.12" +2*30" 2.48" 3.54" 4-78' 8.20" 12.90" 16-52'49" 55" 58" 69" 103.5" 125" 145" 168" 199"20.32" 23.70" 25.34" 31.86" 43.34" 46.80" 47.90" 48.30" 45.16"Temp . 15O 24" 25' 26.5" 28" 32" 39" 43" 50"ayi56" 58" 69" 73" 104" 125" 143" 169" 199"... - 24-82" - 6.00" - 5.06" - 3-34" - 0.76" + 5.10" 14.24" 21.48" 29.20"36-42" 37.48" 49.42" 50.90" 72.20" 79-20' 81.04" 81-90' 76.10"A cetat e of d-l-Naph t hyl.n.hexylcarbinol .Temp ................19.5" 54" 90" 132"D: ..................... 1.0266 1.0001 0.9699 0-9371Temp .......... 21" 47" 83" 104" 123" .. ............... +24.56. 29-90" 34-58' 36.68. 37-58"Temp .......... 21" 49" 83" 104" 123"Temp .......... 21" 49" 83" 104" 123"Temp .......... 21" 49.5" 83" 104" 123"a, i ............... +54.88" 67.42" 78.30" 82.18" 85-00"aYellow ......... + 25.96" 31-54' 36-50' 38-26' 39.68.ugr ............... 29.72" 36.50" 42.00" 44.10" 45.66"Temp .......... 20-5"D: ............. 1.0144Temp .......... 24"a,, ............... + 29-96"Temp .......... 24"Temp .......... 24"ayellow ......... + 31.42"agr ............... + 36.26"Temp ..........24"avi ............... + 67.80"56"0.988554"35.32"52"36-56'52"51"42-46"79-00"Y r o pio n a t e .94"0-957468"37.08"75"39-30'76"45-86'76"86-10"134"0-920897"39.88"96"41.80"96"48-04"96"90.30"154" 185"158" 195"38-64' 38-60"40.58" 39-70"153" 190"46.90" 46.00"158" 190"87.20" 86-70'123' 153"41.00" 41-40'123" 152"42-70" 43-34'123" 152"49-46' 50.24'123' 152'92-96" 94-16"190'41.22'190"42-94'190"49-80'190"93.48OF ROTATORY POWER ON CHEMlCAL CONSTITUTION . 2663u . B 11 t y?W t e .Temp .......... 18" 61" 07" 134-5"Temp .......... 20" 30" 60" 85" 105" 121" 163" 195"a,. ............... i-27.12" 28-94" 32-78O 34.86" 35.92" 36.28" 36-76' 36.42"D: ............ 1.0066 0.9739 0.9459 0.9156Temp ..........20" 57" 85" 105"uRr ............ +32-70" 39.54" 42.50" 43.60"~ ~ ~ l l ~ \ ~ ......... +28-30° 34.26" 36.60" 37.78"Temp .......... 20" 56" 84" 105"avi ............... + 60.50" 73.70" 79.20" 81.90"11- Vnlera t P .Temp .......... 20.5" 56.5" 93" 132"Temp .......... 23" 45" 65" 87"Temp .......... 23" 47" 87" 120"Temp .......... 23" 47" 87" 121"a+ ............... + 27.28" 31.22" 35.48" 37.26"Temp .......... 23" 47" 87" 122"a , , ............... + 50.70" 65-80" 66.42" 69.84"D: ............ 0.9956 0.9694 0.9410 0.9088a ,. ............... +22-58" 25-68" 27.68" 29.38"are]low ......... + 23.68" 27.01" 30.74" 32.26"121"38.18"44.34"121"82.78"119"30.72"138"32-56"138"37-66"138"70.58"163"38-56'44-60"163"83.66"138"31.10"182"32.33"182"37-38"182"70.08"195"38-18"44.02"195"82.46"182"30.90"170"n -1Z ex oa t e .Temp .......19" 570 97" 146"D: ......... 0-9897 0.9636 0.9285 0.8911Temp ....... 20" 48" 60" 72" 107" 130" 152" .. ............ +20.90. 24.36. 25.30" 25.90" 27.40" 27.80" 28-14" 28.16"Temp ....... 20" 49" 58" 76" 109" 129" 153" 170"u3-,,1,~..,, ...... +22*12" 25.80' 26.46" 27.68" 29.16" 29.35" 29.70" 29.74"n.Heptoate .Temp ................... 18" 53.5"Temp ................... 20" 56"Temp ................... 20" 53"ayellow .................. + 20.24" 23-66"D: ........................ 0.9825 0.9584a, ........................ +19*30" 22.66"Temp ...................20" 52"agr ..................... f23.28 26.76n-0 ctoa t e .Temp ................... 18" 55"D: ..................... 0.9806 0.954997"0.922082"24.18"87"25-40'86"28.88141"0-8874114' 148"24-84" 24-92"116" 148"26-04" 26.14"117" 148"29.82" 30*00"92" 144-5"0.9263 0.88808 T. 2664 TNVESTIGATIONS ON DEPEKDENCE O F ROTATORY POWER. E:TC .ri-Octoate (continued) .Temp . . . . . . . SO" 44" 58" 69' 88" 120" 143" 172"a. ............ -f-20.70" 22-94" 23-84" 24.36" 24.80" 25.50" 25.34' 25.04"Temp .......... 20" 45" 68" 91" 118" 143"agr ............ +24*94" 27.88" 29.84" 29.96" 30.74" 30.68"Temp .......... 20" 45" 67" 90" 117" 143"a).eli,,,r ......... +- 21.66" 24-24' 25-80' 26.00" 26.76" 26.62"a. i ...............+46-60° 52.28" 55.74" 56.48" 57-60" 57.60"n-Nonoa t e .Temp .... 17" 59" 95" 144-5"D: ......... 0.9731 0.9412 0.9157 0.8800Temp . . . . 18" 36" 77" 98"Temp .... 18' 58" 7 1" 101"Temp .... 18" 60" 74" 101"a,. ...... f18.30" 20.20" 21.92" 22.40"ayellow ... +l8*92" 22.00" 22.60" 23.24"aqr ......... 9".00" 25.60" 26.26" 27.00"n-I., e c oa t e .Temp . . . . . . . . 20.5" 58" 94"Temp . . . . . . . . 20" 56" 95"a.. ............ +16.60" 19.00" 20.40"Temp . . . . . . . . 20" 49" 95" . ........... -+ 17.54" 19.38" 21.18"as. ............ 20.16" 22.46" 24.44"DI ............ 0.9674 0.9410 0.9137n.Uizdecoate .Temp . . . . . . . . 20.5" 58" 94"Temp ........ 20" 61" 94"ayeii ............ + 16-42' 18.94" 19.84"D: ............ 0.9605 0.9341 0.9075a, ............ +15.80° 18.36" 19.22'agr ............... +19.00" 21.74" 22.54"136'22.60"136"23.64"136"27.38"132"0.8832133"133"20.78"21.60"35.00"133"0.8793172'26.26"30.36"163"22.44"164"23.40'164"27.10"A ce tn t e of l-l-Napht hylme t hylcarbit7ol .Temp ....... 16" 64" 99" 138"D: ............ 1.1071 1.0699 1.0380 1*0010Temp . . . . . . . 27" 36" 56" 100" 136" 160"a, ............ -38.66" 41.84" 46.90' 54.80" 56.70" 57.00"Temp ....... 19" 27" 36" 61" 78" 101" 136" 162"agT ............ -42.70" 47.02" 60.10" 58.32" 62.26" 66.84" 68.60" 69.00"Temp ....... 27" 34" 62" 76" 100" 136" 164"a\i ............ -887.30" 91.90" 110.30" 115.30" 126.00" 129.66' 130-30CSRROXYLIC AClDS DERIVED FlZOill CTCLOBUTANE, ETC. 26635In every case these esters were found to have undergone noracemisatioii during the heating i n the polariineter tube, whilst allof them when hydrolysed yielded samples of the carbinols ofrotatory power identical with hhat of the original, preparations.The authcrs have much pleasure in acknowledging the ableassistance given t o them by 1LI.r. John Ranson, and desire to expresstheir thanks t o the Government Grant Committee of the RoyalSociety for grants which have defrayed some of the expense of thisinvestigstion.MUKICIPAL TECIISICAL SCHOOL.B I, .\ C I i B U KS