1210
VOL.
NOTES
the benzene solution were stirred with warm 10% aqueous sodium hydroxide solution for 15 min. and extracted with benzene, which removed the unchanged nitrile IV. The alkaline solution was acidified with cooling, and the oil which separated extracted with benzene. From the eutract, the trans-acid could be removed by means of 5% aqueous sodium carbonate solution, while the cz+lactone I1 was obtained by distillation of the benzene solution. B.p. 145148' (20 mm.). And. Calcd. for C8H1:02*C, 68.6; H, 8.6. Found: C, 68.6; €I, 8.7. The trans-acid, eventuallg- obtained by acidification melts st 106'.' The results of the experiments ale summarized in Trtblr I.
rrmx
I
ACID HYDROLYSIS OF THE SITRILE IV
Product (in yo of theory)
Hydrobromic Acid after 2 4 7 13 2 4 10 4 10 hr. hr. hr. hr. hr. hr. hr. hr. hr.
Lactonesa cis-Lactone (TI) trans-I11
15 30
l-
26
Acid m.p. 117' Starting material (IV) Cnsatiirated amidesb Acids containing bromine
Surfuric Acid after
Hydrochloric Acid after
23
24
22
2
5
1
8
8 21
4
10
5
13
30
I5
30
8
73
15
a Total amount of lactones, when no separation of the isomers was carried out. See text.
23
which would make it useful as an analytical re, ~ for the study agent for nickel and p a l l a d i ~ mand of the complexes formed between nickel and the vic-dioxime in basic ~ o l u t i o n , ~4-carboxy-1,2-~~ cyclohexanedionediolnie was prepared in this Laboratory. The synthesis of 4-carboxy-1,2-cyclohexanedionedioxime involves the following steps: the high pressure hydrogenation of et hyl-4-hydroxybenzoate to 4ethoxycarbonylcyclohexano1, the oxidation of this alcohol by the acid-chromate method to 4ethoxycarbonylcyclohexanone, the selenium dioxide oxidation of the monoketonr to 4-ethoxycarbonyl-l,2-cyclohexanedione,the oximation of the dione to 4-ethoxycarbonyl-1,2-cyclohexa1i~dionedioxinie, and hydrolysis of this dioxime to the desired compound, 4-carboxy-1.2-cyclohexanedionedioxime. ilqueous oximation of 4-ethoxycarbonyl-l,2cyclohexanedione using potassium hydroxide and hydroxylamnionium chloride gave as the major product 4-hydroxyaminocarbonyl-l,%cyclohexanedionedioxime rather than 4-ethoxycarbonyl-l,2cyclohexanedionedioxiine. 4-Hydroxyaminocarbonyl-l,2-cyclohexanedionedioximecan also be conveniently prepared from 4-ethoxycarbonyl-1 ,% cy clohexanedionedioxime. The pK values mere determined for the three acidic hydrogens of 4-carboxy-1,2-cyclohexanedionedioxime and the following results were obtained: pKl = 4.86, PIG = 10.45 and pK3 = 12.37. EXPERIMESTAL
Reaction of sulfurtc ncad with IT. To 20 g. of IV in 150 ml. of acetic acid, 100 ml. of 10% sulfuric acid was added and the reartion mixture was treated as above. I n this case, the neutral product had m.p. 135-152' and showed the same' elementsry analysis as the amide of V.4 In the, acidic fraction a product m.p. 117' wab found. Reactzon of I-cUclohexenP-i-acetzc acid (V) with sdjurt( acid. To 4.5 g of the acid V in 35 ml. of glacial acetic acid, 25 ml of 50% sulfuric acid was added and the mixture wac refluxed for 4 hr. Water was added and the product worked up as urual Distillation of the benzene layer gave 2.5 g (55%) of the cis-lactone 11, b.p. 140-150' (20 mm.). Ail unidentified acidir product (1 g.), b.p. 180-200' (20 mm ), was also found. DEPAILTMEST OF ORGAXIC CHEMISTRI THEHEBREW UNITERSITY
~-12ltho~ycarbonylcyclohezanol. 4-Ethoxycarbonylcyclohexanol has been prepared by Gngnade and M0rriss.1~ Equally satisfactory results were obtained by the following procedure. One hundred grams of ethyl-4-hydroxybenzoate and 15 g. of a 2% galladinm ratalystI5 on a strontium car(1) No. SS in a series on "Chemistry of the czc-Dioximes." Previous paper in this series is So. X I S , J . Org. Chena., 21, 815 (1956). ( 2 ) Contribution S o . 5%; work was performed in the hmes Laboratory of the U S. Atomic Energy Commission. (3) R. C Voter and C. T'. Banks, Ann1 Chem., 21, 1320
(1949). (4) N. H. Furman and B. McDuffie, L-. S. dtomzc Energy Comm., M-4234 (1947). ( 5 ) 31. Hooreman, Anal. Chzm. Actu, 3, 635 (1949). (6) -4.K. Babko, Zhur. il'eorg. Khim.. 1 , 485 (1956). JERUSALEM (7) A. K. Babko, Zhur. Anal. Khim., 3, 384 (1948). (4)0.Wallnch, AnTL,, 353, 292 (19Oi), n1.p. 153". (8) E. Booth and J. D. H. Strickland, J . Am. Chent. Soc., 75, 3017 (1953). (9) F. Feigl, Ber., 57, 759 (1921). (101 A. OkG and M. Polster, Collectzon Czechoslov. Cheni. Preparation of 4-Carboxy-1,2Conmuns., 13, 561 (1948). (11) A. OkitE: and BI. Polster, Collectzon Czechosloo. Chsm. cpclohexanedione Dioxime1t2 Cunzntzms., 13, 572 (1948). (12) P. Wulff and A. Lundberg, 2. Ver. deut. Chem., Beih., CHARLES V. B.4m.5, J. P. LAPLANTE, ASD JOHN J. RICHARD KO.48, 76 (1944); Chent. Abstr., 41, 7303d (1947). (13) K. B. Yatsimirskir and Z. W. Grafova, Zhur. ObshcheZ Khim., 23, 935 (1953). Received January 13, 1968 (14) H. E. Ungnade and F. V. Morriss, J . Am. Chent. SOC.,70, 1898 (1948). In an effort t o find a vic-dioxime which was water (15) R. H. ?IlRrtin and R . Robinson, .I Chm Sor., 491 soluble and still possessed the desired properties (1943).
AUQUST 1958
NOTES
1211
bonate support were suspended in 150 ml. of pursed Anal. Calcd. for C?HllN3O4: lrj, 21.00%. Found: N, dioxane, and the material was reduced at a hydrogen pres- 21.10%; 20.81%. sure of 1800 p.s.i. a t 150" for 4 hr. in a Parr high-pressure 4-~a~boxy-l,&cyclohexanedionedzozzme. 4-Carboxy-1,2apparatus. The reaction mixture was filtered, the dioxane cyclohexanedionedioxime was obtained by hydrolysis of removed by distillation and the 4ethoxycarbonylcyclo- 4-ethoxycarbonyl-l,2-cyclohexanedionedioxime. This was hexanol was vacuum-distilled through a 50-cm. Vigreux accomplished by heating on a steam bath for 1 hr. a mixture column. Yield of Pethoxycarbonylcyclohexanol, 80%; b.p. of 0.1 mole of the ester, 0.15 mole of potassium hydroxide, 115-123" (4 mm.); n y 1.4635. and 125 ml. of water. After cooling, the reaction mixture 4-Ethoxycarbonylc~clohexanone. 4Ethoxycarbonylcyclo- was acidified t o pH 1-2. The precipitated acid was filtered hexanol was oxidized by the acid-dichromate method,16 but and dried. More acid can be obtained by extraction of the because of possible hydrolysis of the ester grouping, the usual hydrolysis mixture with diethyl ether. The acid was reprocedure way slightly modified in that the temperature was crystallized by dissolving in a minimum amount of hot not allowed to rise above 35". The crude 4-ethoxycarbonyl- dioxane, adding petroleum ether to incipient cloudiness, cyclohexanone was vacuum-distilled through a 50-cm. cooling, and filtering. The acid had a puritv of 95% based Vigreux column and the product was collected. Yield of on micro Dumas nitrogen determinations and titration of 4-ethoxycarbonylcyclohexanone, 65%; b.p. 112-118" (4 the carboxy hydrogen. mm.); n'," 1.4594. Further purification can be obtained by dissolving ap4-Ethoxycarbonyl-1,I-cyclohexanedione.The 4-ethoxycar- proximately 2 g. of the acid in 50 ml. of dioxane and passing bonylcyclohexanone was oxidized with alcoholic selenium the solution, while hot, through a column 10 cm. in length dioxide to give the corresponding diketone. The method and 2.5 cm. in diameter which was packed with a 1 : 1 mixreported by Riley, Morley, and Friend" as modified by ture of acidic and basic Woelm alumina. This procedure was Hach, Banks, and Diehlls was employed. The reaction repeated twice and a very pure compound was obtained, as mixture was filtered and fractionated through a 50-cm. indicated by titration of the acid which gave a molecular Vigreux column under reduced pressure. The dione is very weight of 186.16; theoretical is 186.17.Yield of 4-carboxyunstable towards prolonged heating and the distillation 1,2-cyclohexanedionedioxime,50%; m.p. 218-220" with deshould be completed as rapidly as possible. Yield of 4- composition. ethoxycarbonyl-1,2-cyclohexanedione,48%; b.p. 120-135" Anal. Calcd. for C7H10A-201: iY, 15.05%. Found: S, (2mm.); n': 1.4862. 15.08%; 15.04%. $-Ethoxycarbonyl-1,2-cyclohexanedionedioxime.4EthoxypK Determinations. The molar dissociation constants for carbonyl-1,2-cyclohexanedionewas oximated by a method 4-carboxy-1,2-cyclohexanedionedioxime were determined by very similar to that of Bachmann and Boatner.10 One-half the following methods. The pK1' for the carboxy hydrogen mole of the dione, 2 moles of hydroxylammonium chloride, was determined by direct titration with 0.1N potassium 4 moles of pyridine, and 600 ml. of absolute alcohol were hydroxide after having added a known excess of standardrefluxed for 35 min. on a steam bath. After most of the ized 0 . W hydrochloric acid. A value of 4.75 ( p = 0.100) pyridine had evaporated, the oily mixture was poured into was found. Conversion to the thermodynaniic constant, an equal volume of cold water to precipitate the crude pK1, by application of the Debye and Huckel theory, gave 4ethoxycarbonyl-l,2-~yclohexanedionedioxime. This mate- a value of 4.85. rial was dried and recrystallized twice from ethyl acetate. The method of Banks and Carlson22 was used to deterYield of 4-ethoxycarbonyl-1,2-cyclohexanedionedioxime1mine the pK values of the oxime hydrogens. The average 55%; m.p. 167". value found for four determinations of pK,' was 10.44 ( p = Analytical samples were obtained by dissolving 1 g. of 0.01) and for two determinations of pK3' was 12.31 ( p = the ester in 50 ml. of absolute ethanol and passing the 0.06). Conversion to the thermodynamic constants gave solution through a column 10 cm. in length and 2.5 cm. in 10.45 for pKz and 12.37 for pK3. diameter packed with Woelm basic alumina. Ethanol was Due to the hydrolysis of 4-hydroxyaminocarbonyl-1,2used as the eluant. The 4ethoxycarbonyl-1,2-cyclohexane- cyclohexanedionedioxime the pK values were not deterdionedioxime was precipitated from the ethanol by the mined. addition of petroleum ether, filtered, and dried at 110" for INSTITUTE FOR ATOMIC RESEARCH AND 1 hr. DEPARTXENT OF CHEMISTRY Anal. Calcd. for CgHl4Nz04:N, 13.08%. Found: K, IOWA STATECOLLEGE 12.97%; 13.15%. AMES,IOWA $-Hydrox~a~minocarbot~yl-1,2-cyclohexanedwnedioxi~. 4 Hydroxyaminocarbonyl-1,2-cyclohexanedionedioxime can be (22) C. V. Banks and A. B. Carlson, Anal. Chim. Acta, 7, prepared from 4-ethoxycarbonyl-l,2-cyclohexanedionedioxime by using the synthesis given for benzohydroxamic 291 (1952). acid." This compound gave a red precipitate with nickel while cupric racetate produced a greenish-blue color characteristic of hydroxamic acids. It was observed that this Reactivity Ratios of hydroxamic acid was hydrolyzed readily by aqueous acid solution, which is in agreement with the information reTrifluoromethyl-substituted Styrenes with ported in the review paper by Yale.21 Yield of 4-hydroxyaminocarbon~l-1,2-cyclohexanedionedioxime 60%; m.p. Methyl Methacrylate and Styrene 152'. L. E. COLEMAN, J R .AND ~ W.S. DURRELL (16) J. E. Nickels and W. Heintzelman, J. Org. Chem., 15, 1142 (1950). Received January 21, 1958 (17) H.L. Riley, J. F. Morley, and N. A. C. Friend, J. Chem. SOC.,1875 (1932). (18) C. C. Hach, C. V. Banks, and H. Diehl, Org. SynTo find the effect of substitution of the tritheses, 32, 35 (1952). Auoromethyl group on the polymerization re(19) W.E. Bachmann and C. H. Boatner. J . Am. Chern. activity of styrene, the reactivity ratios of 3Soc., 58,2097 (1936). (20) C.R. Hauser and R. R. Renfrow, Jr., Org. Syntheses, Col. Vol. II, 67 (1947). (1) Present address: The I.uhrizo1 Corporation, Cleve(21) H. L. Yale, Chem. Reus., 33, 209 (1943). land 17, Ohio.
