2540
C. M. GREER A N D ROGER ADAMS
VOl. 52
Anal. Subs., 0.2069: COz, 0.6068; H20, 0.1016. Calcd. for CI6Hl2O2:C, 80.32; H, 5.39. Found: C, 79.99; H, 5.49. Decomposition of 4-Hydroxyphenyl-styryl Ketone.-Ten grams of this chalcone was refluxed with 200 CC. of 50% aqueous potassium hydroxide for eight hours. Ether extraction of the alkaline solution yielded a small amount of benzaldehyde, b. p. 175B O " , which was identified by means of its phenylhydrazone;" m. p. 153-154'. A very small amount of benzyl alcohol was also obtained. This was undoubtedly produced by the Cannizzaro reaction. The alkaline solution produced a brown precipitate on acidification which was dissolved in dilute alkali. The solution was saturated with carbon dioxide which caused the separation of some unreacted chalcone along with some amorphous polymerization products. These were filtered and the filtrate was extracted three times with 100-cc.portions of ether. The ether was distilled and the residue recrystallized from a small amount of water. Crystals of p-hydroxyacetophenone melting a t 107" were obtained. It was identified by means of a mixed melting point and conversion t o the phenylhydrazone,'* which melted a t 135-136 '.
Summary Concentrated potassium hydroxide splits simple chalcones into the corresponding aldehyde and ketone. The best conditions for accomplishing this degradation and procedures for isolating the products are given. URBANA, ILLINOIS [CONTRIBUTION FROM THE CHEMICAL LABORATORY OF THE UNIVERSITY OF ILLINOIS]
PREPARATION AND BACTERICIDAL PROPERTIES OF CERTAIN PENTADECANOIC, HEPTADECANOIC AND NONADECANOIC ACIDS. XIX' BY C. M. GREERAND ROGERADAMS RECEIVEDMARCH10, 1930
PUBLISHED JUNE6, 1930
I n two previous papers covering the preparation and properties of certain dialkyl acetic acids, i t was demonstrated that the hexadecanoic acids were more effective bactericidally t o B . Leprae than the octadecanoic acids, and far more effective than the dodecanoic, the tridecanoic or the tetradecanoic acids. Representatives of the missing series, pentadecanoic, heptadecanoic and nonadecanoic acids have now been prepared. The bacteriological results of the specific compounds produced are given in Table I. It is obvious that the C15 and the C17 acids are not as effective as the CIS, and the C19 acids are less effective than the previously prepared Cl8 acids. From the tables containing the data for all of the acids from Clz to C19, i t may be concluded that the bactericidal action is zero for the Clz acids, and practically nil for the C13 acids. Beginning with the C14 acids the '1 l2
Biltz, Ann., 305, 171 (1899). Nencki, Rer., 30, 1770 (1897). The previous paper in this series is XVIII, Armendt and .4dams, 52, 1289 (1930).
June, 1930
Clj, C16 AND
2541
Cir ACIDS AND B. L E P R A S
TABLE I BACTERIOLOGICAL TESTSTO B. Lefirae Dialkyl acetic acids containing CIS, C1; and CN Dilutions of sodium salts in thousands 5
25
50
74
62
85
100
125 155 192 250
333
+ + + * * * * +
+ + + + * * + + + + + + * + + + + + + + * + + +
+ + + + + +
I’entadecanoic Acids
C H ~ C H ( C O ~ H ) C ~ Z H Z ~ - U- - - C ~ H ~ C H ( C O Z H ) C I I H ~ ~ -_~ ~ - _ - - CaH?CH(CO%H)Ci oH~i-9~ i C4HgCH (C02H)CsHig-n - - - - - * CjHiiCH(C02H) CsH1r-n i C ~ H I ~ C H ( C O ~ H ) C ~ H I ~ -_~ _ _ _ - Heptadecanoic Acids CH~CH(CO~H)CI~H~~-~ - - - - CzHsCH(COzH)Ci3H2r-n CaH;CH(C02H) CnH26-n - - CdHgCH(C02H)CiiHzr% - - - - - - _ CaHiiCH(C02H) CIO H ~ - n C B H I ~ C H ( C O ~ H ) C ~ H ~ ~-~ - - - - - C;HibCH(COzH)CsHi;-n
- - * * * + + + + + + + * + + + + + + + * + + + + + + + * + + + + + + + * * + + + + + * + +- +- + + + + + * + + + + Nonadecanoic Acids
- + + + + + + + + + + + - + + + + + + + + + + + - + + + + + + + + + + +
C~H;CH(CO~H)CI~HZ~-~ C~H~~CH(CO~H)C~ZH~~-~ CrHisCH(C02H)CIaHzi-n
effectiveness reaches a maximum in the c 1 6 series, then drops off with a certain irregularity t o a very low bactericidal value in the CN acids. Apparently the best combination of physical properties which are presumably causing the bactericidal action, appears in the hexadecanoic compounds. In Table I1 are given bacteriological results on individual members of the Clz to CI9acids tested all a t one time. The maximum in the hexadecanoic acid is clean cut. The various acids were prepared in a manner similar t o those previously described from the proper disubstituted malonic esters. TABLE I1 BACTERIOLOGICAL TESTSTo B. Leprae.
SERIESO F DIALKYLACETICACIDS, c12-cI9
No. of C atoms
12 13 14 15 16
17 18 19
5
Dilution of sodium salts in thousands 155
250
500
- + + - + - + + - + + +
+ + + + +
+ + + + + +
50
100
+ + + + + + - + + + + + -
-
-
2542
Vol. 52
C. M. GREER A N D ROGER ADAMS
Experimental Part TABLE 111 CONSTANTS OF ESTERSAND ACIDS Compound
B. p.,
Found, % H
dy
:n
O C .
C
Diethyl dialkyl malonates (all alkyl groups normal) CH~C(COZC~H~)ZC,~H 161-164 ~~ (1.5-2.5 mm.) 1.44120.9217 C2HbC(COzCzHs)zCiiH23 150-154 (0.2-1.O mm.) 1.4420 ,9262 CSHIC(COzCzHs)tC10H21 143-148 (0,l-1.0 mm.) 1.4416 .9256 C~H&!(COZC~H~)ZCBHLB 143-147 (0.1-1.0 mm.) 1.4420 ,9241 CsH11C(C0zC~H6)zCsHI~ 142-146 (0.1-1.0 mm.) CaH13C(C02CzHa)2C7H15 146-152 (0.1-1.0 mm.) 1.4412 ,9231 Calcd. for each isomer of C20H3804.., . . . . . . . . . . . . . . . . . . . . . . , , ,
.
70.01 70.16 70.02 69.95 70.28 70.14 70.11
11.1 11.25 11.12 11.19 11.17 11.18 11.19
74.66 74.24 74.32 74.20 74.20 74.38 74.31
12.58 12.42 12.51 12.46 12.37 12.55 12.48
Pentadecanoic Acids CH~CH(COZH)CIZH~~ CiHsCH (COzH)CiiHzs CsHCH(C0zH)CioHu C~HOCH(CO~H)COHIB CbHiiCH(C02H) CsHi7 CsHiaCH(COzH)C7H1a Calcd. for each isomer OF
172-175 (2-3mm.) m. p. 34-36 160-163 (2-3 mm.) 1.44550.8821 164-167 (2-3mm.) 1.4450 ,8819 159-162 (2-3mm.) 1.4459 ,8824 161-164 (2-3mm.) 156-159 (1-2mm.) 1 4450 ,8806 ClbH3002... . . . . . . . . . . . . . . . . . . . . . . , . . I
TABLE IV CONSTANTS OF ESTERSAND ACIDS Compound
Found, % H
d;'
B . p., OC.
C
Diethyl dialkyl malonates (all alkyl groups normal) C H ~ C ( C O ~ C ~ H S ) ~ C I J172-176 ~~ (0.5-1,O mm.) 1,44360.9164 C2H6C(C0~CzHs)zC~~H17 178-181 (0.8-2.0 mm.) 1.4435 .9207 C~H,C(COZC~H~)~CIZH 173-177 ~~ (0.5-1.0mm.) 1.4438 .9191 C4HoC(C0~C2H5)2CnH23 171-176 (0.5-1.0 mm.) 1.4439 ,9173 CSH~~C(CO~C~H~)~C 148-154 I O H ~(~0 . 1 4 . 8 mm.) csHiac(co,c,H6),cgHi, 170-174 (0.5-1.5 mm.) 1.4441 ,9178 C7HlsC(C02C2H5)2CsHl7 157-161 (0.2-1.0 mm.) 1.4436 ,9171 Calcd. for each isomer of C22H4204.. . . . . . . . . . . . . . . . , , , , . . , , . .
.
.
71.20 70.95 71.33 71.21 71.31 71.20 71.40 71.29
11.53 11.33 11.40 11.42 11.35 11.39 11.36 11.43
Heptadecanoic Acids
75.77 12.67 174-177 (1-2mm.) m. p. 45.547.5' 164-168 (1-2mm.) 1.44800,8810 75.27 12.68 183-187 (2.5-3.5 mm.) 1 ,4483 ,8827 75.63 12.72 174-177 (2-3 mm.) 1.4484 ,8783 75.35 12.61 75.94 '12.50 177-182 (2-3mm.) 182-185 (2-3mrn.) 1.4489 .8821 75.31 12.59 184-187 (2-3mm.) 1.4483 .8780 75.44 12.71 C I ~ H ~ ~ .O. .Z. .. .. . . . . . . . . . . . . . . . . . . . . . 75.48 12.68 M.p. 54" according to Morgan and Holmes, J . Soc. Chem. Ind.,46, 152 (1927).
CHaCH(COzH)Ci4H29 C&~CH(COSH)CUH~ CaHrCH(CO2H)CuHzs C~HOCH(COZH)CIIH~~ CIH~ICH(COZH)CIOHZI CsHiaCH(COzH)CsHi9 C~HI~CH(COZH)C~HU Calcd. for each isomer of a
June, 1930
2543
THE REDUCTION OF NICOTINE
TABLE V
ESTERS AND ACIDS
CONSTANTS OP
dy
:n
B. p.. “C.
Compound
Pound, % C H
Diethyl dialkyl malonates (all alkyl groups normal) C3H7C(COzCzH5)zC14H29 180-184 (0.2-1.0 mm.) 1.4459 0.9141 CsHllC(C02CzH6)zClzHz5 178-181 (0.2-1.0 mm.) 1.4460 ,9112 C7H15C(C0zC2H6)ZC10H21182-186 (0.2-1.0 mm.) 1.4459 ,9116 Calcd. for each isomer of CZ4H4604.. ...........................
72.29 72.30 72.23 72.29
11.63 11.58 11.71 11.64
Nonadecanoic Acids 182-185 (0.5-1.5 mm.) m. p. 35-37 184-188 (0.5-1.5 mm.) 1.4508 0.8752 180-184 (0.5-1.5 mm.) m. p. 31.5-33.5 C19H380z.............................
76.56 76,47 76,65 76.43
12.81 12.85 12.81 12.84
CaH7CH(COzH)CirHzg CsHiiCH (COzH)CizH25 C7HisCH(COzH)CioHzi Calcd. for each isomer of
Summary A number of pentadecanoic, heptadecanoic and nonadecanoic acids have been prepared and tested bacteriologically toward B. Leprue. The C15 and the CI7acids are active but not to such a degree as the previously studied hexadecanoic acids, The C18acids are very slightly bactericidal. URBANA, ILLINOIS [CONTRIBUTION FROM THE CHEMICAL LABORATORY
UNIVERSITY OF
OF THE
ILLINOIS]
THE REDUCTION OF NICOTINE AND SOME DERIVATIVES OF HEXA- AND OCTAHYDRONICOTINES BY WALLACE WINDUSAND C. S. MARVEL PUBLISHED J U N R 6, 1930
RECEIVED MARCH 10, 1930
Nicotine (I) should be the cheapest basic product for the preparation of a piperidine ring with an unsaturated side chain in the beta position (IV), provided the following reactions proceed in the normal manner.
-
CH2-CHz
1
1
/‘-cH
1 I
CH1
I
I
CH3 CHz
I
1
I
I
CH2 CHa \N/ €I I1 CHz-CHz
A I CHz CH-CH I
CHz-CHz
CH2 CH-CH
I
\N/
\N/
CH2
/\
reduction
\N/
I
CH2
CH2
\N/
Acylation
I
CHI exhaustive
methylation
CHz CH-CH=CH-CH=CH, I
I
C€Iz CHz \N/ I11 ‘CHa \COR
The reduction of nicotine by means of sodium and alcohol was first studied by Liebrecht,’ who isolated a basic product which he called diLiebrecht, Ber., 18, 2969 (1885); 19, 2587 (1886).
