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April 20 , 1952 NOTES 2111

(CY - carbethoxy - a! - cyanomethylene) - 1,4 dihydro-quinoline. Diethyl malonate, ethyl acetoacetate,ethyl phenylacetate and acetonitrile failed toyield products analogous to I1 under similar re-action conditions.

Experimental6

Reaction of I-Methylquinolinium Iodide with Malononi-tri1e.-To a mixture of 13.6 g. (0.05 mole) of l-methylquino-linium iodide, m.p. 146', 3.3 g. (0.05 mole) of malononi-trile and 100 ml. of absolute ethanol, cooled in an ice-bath,was added with vigorous stirring a solution prepared from2.3 g. (0.10 gram atom) of sodium in 50 ml. of absoluteethanol. The stirring was continued for 3 hours, and thenthe mixture was allowed to stand overnight. The productwas isolated by filtration. Two recrystallizations from abso-lute ethanol gave 1.1g. (10%) of material crystallizing asfine yellow filaments, m.p. 291.5-292.5".

Anal. Calcd. for ClaHgNS: C, 75.35; H, 4.38; N, 20.28.Found: C, 75.12; H , 4.17; N, 20.30.

The infrared spectrum showed strong absorption in th enitrile region, a t 2197 and 2176 ern.-', and indicative of con-jugation with the nitrile groups, also a band a t 1625 ern.-'and a double band a t 1619-1620 cm.-'.l-Methyl-4-(~,~~-dicyanomethylene)-l,4-dihydroquinoline(IIb).-l-Methyl-4-chloroquinolinium iodide, prepared byheating 4-chloroquinoline7 under reflux with excess methyliodide,s was recrystallized from ethanol as yellow needles,m.p. 204-206'. A mixture of 1 .3 g. (0.004 mole) of 1-

methyl-4-chloroquinolinium iodide, 0.3 g. (0.004 mole) ofmalononitrile a nd 75ml . of absolute ethanol was cooled in anice-bath. A solution of sodium ethoxide prepared from 0.1g. (0.004 gram atom) of sodium and 50 ml. of absolute eth-anol was added with vigorous stirring. The reaction ap-peared to tak e place immediately bu t stirring was continuedfor 8 hours to ensure completeness of reaction. The prod-uct was collected by fi ltration, and th e yield was quant ita-tive. Two recrystallizations from ethanol gave yellowfilaments, m.p . 291.5-292', which did not depress the melt-ing point of th e CIJHgNaproduct obtained from l-methyl-quinolinium iodide and malononitrile. The infrared spectrawere also identical.

Reaction of 1,2-Dimethylquinolinium Iodide with Malono-nitrile. 1,2-Dimethyl-4-(a,~~-dicyanornethylene)-1,4-dihy-droquino1ine.-To a mixture of 14.2 g. (0.0: mole) of 1,2-dimethylquinolinium iodide, m.p. 195-196 , 3.3 g. (0.05mole) of malononitrile, and 100 ml. of absolute ethanol,cooled in an ice-bath, was added with vigorous stirring asolution prepared from 1.2 g. (0.05 gram atom)of sodium in 50ml. of absolute ethanol. Stirr ing was continued for 4 hoursand the reaction mixture was allowed to stand a t 25' for anadditional 4 hours. The product was isolated by filtrationand was recrystallized from absolute ethanol as yellowneedles, m.p. 267.5-268'; yield 3.8 g. (34%).

Calcd. for CldH11Na: C, 76.00; H, 5.01; N, 18.99.Found: C, 76.16; H , 5.26; N, 19.14.

l-Methyl-4-(a-carbethoxy-cr-cyanomethylene)-l,4-dihy-droquinoline (IIc) -This compound was obtained fromequimolar quanti ties of 1-methylquinolinium iodide, ethyl

cyanoacetate and sodium ethoxide, following the same direc-tions as those given in th e preceding paragraph. Theproduct was isolated as yellow needles from ethanol, m.p.181.5-182.5'; yield 2.9 g. (23%).

Anal. Calcd. for CXHUN~OZ:, 70.84; H, 5.55; N,11.02. Found: C, 70.86; H, 5.66; N, 11.10.

The infrared spec trum showed strong absorption a t 2189cm.-', indicative of nitrile, and 1671 cm.-l, indicative ofcarbonyl, as well as bands at 1624 and 1617 cm.-', similarto those exhibited by IIb.1,2-Dimethyl-4-(~t-carbethoxy-~t-cyanomethylene)-l,4-

dihydroquinoline .-This compound was prepared by thesame method, using equimolar quantities of 1,a-dimethyl-quinolinium iodide, ethyl cyanoacetate and sodium ethoxide.

The authors are indebted to Miss

ElizabethM. Petersen fordetermination of theinfrared absorption spec-

tra and to Miss Emily Davis, Mrs. Jean Fortney and Mrs. Katherine

Pih for the microanalyses.

(7 ) B. Riegel, G.R. Lappin, B. H. Adelson, R. I. Jackson, C. 1.

Albisetti, Jr., R. M. Dodson and R. H. Baker, TXIS OURNAL, 68, 1264

(1946).

Anal .

(6 ) Melting points are corrected.

The product was recrystallized from acetone as yellowneedles, m .p 172.5-173.5'.

Anal. Calcd. for CleHleNpOn: C, 71.62; H , 6.01; N,10.44. Found: C, 71.32; H , 6.20; N , 10.25.

Reactions of 1-Methylquinolinium Iodide with Other AC-tive Methylene Compounds.-The reactions of l-methyl-quinolinium iodide with diethyl malonate, acetonitrile andethyl phenylacetate in ethanol with sodium ethoxide failed

to produce any isolable condensation product. The reac-tion of 1-methylquinolinium iodide with ethyl acetoacetatein aqueous sodium hydroxide solution failed to produce thecondensation product described by Kaufmann.* Whensodium ethoxide in ethanol was used, the same result wasobtained.

THENOYESCHEMICALABORATORY

URBANA,LLINOISUNIVERSITY OF ILLINOIS

RECEIVED ECEMBER7, 1951

Spectrophotometric Studies of Complex Formationwith Sulfosalicylic Acid. V. With Chromium(II1)

BYALFREDM. LIEBMANXD ROBBIN . ANDERSON

RECEIVED OVEMBER3, 1951

The reaction of chromium(II1) with sulfosalicylicacid has been studikd as par t of a series of investi-gations on complex formation in solution betweensulfosalicylic acid and ions of various e1ements.l

Figure 1 shows, for comparison, the absorptionspectrum of an equimolar mixture of chromium-(111) nitrate and sulfosalicylic acid and those forcorresponding solutions of each separately. CurveB shows the net difference in transmittance whenthe absorption curve for the mixture was deter-mined using the chromium(II1) as a blank. It isevident that some colored product is formed, witha maximum in absorption at 550 mp. It was also

found that the presence of sulfosalicylic acid in-creased materially the pH a t which precipitation ofchromium(II1) hydroxide could occur.

I I

d ' I I I

t-c 4050!kL50 500 550 600 650

Wdve length (mp).

Fig.1.-Absorption spect ra: A, 0.0025 SSA vs . H,O blank:

B, 1: l Cr(III)/SSA total molarity = 0.005 v s . Cr(II1) blank

(0.0025 M ) ; C, Cr(II1 ) (0.0025 M ) s. HzO blank; D, 1 :1

Cr(III)/SSA total molarity = 0.005 vs . H20blank.

Measurements in solutions of different $H values

showed maximum color intensities in the range of(1) R. T . Foley and R. C. Anderson, THISJOURNAL, 70, 1195

(1948); 71 , 909 (1949); ?a , 5609 (1950); S . E. Turner and R . C

Anderson, i b i d . , 71, 912 (1949).