CARLRil. HILL,HELENI. SCHOF~ELD, ALFREDS. SPRIGGS AND MARYE. HILL
1660
Lipmann and K. Laki for a number of very helpful comments and references.
on pp. 259 and 269. The new constants do not alter any of our qualitative arguments. Acknowledgment.-- \Ye are indebted to Drs. I;.
[ ~ O W " l ' I B U T I OFROM ~ THE
VOl. 7.1
RXCGIVED Ar;bUSr 28, 1950
RBTHESDA, MIL
DEPARTMENT O F CHEMISTRY, TENNESSEE A. AND I. STATE COLLEGE]
The Synthesis, Properties and Dehydrohalogenation of Some a-Phenoxy and 2,4Dichlorophenoxy Substituted Acid Chlorides R u CARL51. HILL, HELENI. SCAOFIELD, ALFREDS. SPRIGCS AND MARYE. HILL This paper describes the synthesis and chemistry of several a-phenoxy and a-2,4-dichlorophenoxy substituted fatty acid chlorides; namely, propionyl, butyryl, valeryl, isovaleryl, caproyl and enanthyl. Although the acid chlorides of both series reacted smoothly with such reagents as ammonia, aniline, phenylhydrazine, ethanol and phenol, there was a noticeable difference in the reactivity of the chlorides of each series with a given reagent.
A previous paper1 reported the dehydrohalogenating action of triethylamine on several phenoxy and chlorine-substituted phenoxyacetyl chlorides.
2,4-dichlorophenoxy substituted fatty acid chlorides. It was observed that the nature of the alkyl and phenoxy group attached to the alpha carbon of
TABLE I PHYSICAL CONSTANTS AND ANALYTICAL DATAOF ACID CHLORIDES B.P.1'
a-Phenoxy
OC.
hfm.
d20C
? >OD l
Found
5 6 7 11 3
1.1865 1.1355 1.1127 1.0885 1.0643
1.5184 1.5138 1.5087 1.5048 1.5025
47.15 52.60 57.00 61.69 66.75
105-106 104-105 109-110 126-127 115-117
Propionyl' Butyryl" Valeryl Caproyld Enanthyl
MRD
Calcd.
47.16 51.78 56.40 61.02 65.63
Yield,
% 73 74 88 88 82
Chlorine,b % ' Found Calcd
Formula
CQHSOZCI CloHllOZCl Ci1H1aOZCl ClzHlsOzCl Ct3H1702Cl
19.28
18.21 16.64 15.99 14.20
19.20 17.85 16.67 15.64 14.77
a-2.4-Dichlorophenoxy
Propionyl 137-139 9 1.3857 1.5475 58.06 56.90 84 C&OeC13 13.91 13.98 Butyryl 145-147 3 1.3516 1.5397 (i2.05 61.52 90 Cl"HoO?Cla 12.86 13.25 \kleryl 160-162 10 1.3078 1,5350 67.01 (itj. 14 *54 Cl,Hi102C13 11.80 12.59 lsovaleryl 145-147 4 1,3028 1.5338 67.15 (Kl4 98 CllH1102C13 12.45 12.59 Caproyl 150-153 3 1.2732 1.5301 71.70 70.76 96 CleH130fiCl3 12.01 12.00 Enanthyl 175-176 7 1.2392 1.5208 76.76 75.38 98 Cl~H1,02Cl, 11.17 11.46 Boiling and melting points are corrected. * Analyzed by potentiometric titration using silver, silver-silver chloride electrodes; %'s refer t o ionizable chlorine. Reported: R. Stoermer and P. Atenstadt, Ber., 35, 3565 (1902); b.p. 115Reported: C. A. Bischoff, ibid., 34, 2127 (1901); b.p. 128-131' (38 mm.). 117' (10 mm.). (1
TABLEI1 PHYSICAL CONSTANTS A N D ASALYTICAI.I ~ A T A FOR AMIDES AND ANILIDES OR ACIDCHLORIDES Amides'i - -
7
a-Phenoxy chloride
Propionylh ButyrylC Valeryl Caproyl Enanthyl
Yield,
%
M . p , , oc.
!IO 45 44 57 87
128-129 118-1 19 114-115 100-102 106-108
Formula
CQHIIOPN C10H1302iX CiiHikOzX C1zH1702X ClsHlsOzN
. ~
Nitrogen, '% Found Calcd.
8.51 8.30 7.65 6.98 6.12
8.49 7.82 7.25 6.76 6.34
-~~~
Anilide5
Yield,
%
X p . , '(2.
31 30 28 24 65
116-116.5 79-81 98-99 93-93.5 84-85
~
Formula
CI~HI~O& CisH17OzN ClTH1802N C18HzlOnN Ctd3z.sOzN
__ ..-.
~
Nitrogen, g., Found Calcd.
6.13 5.38 5.18 4.43 4.65
5.80 5.49 5.20 4.95 4.71
a -2,4-Dichlorophenoxy
97 81-82 CSHc+O~ClzN 5.96 5.98 98 138-139 ClaHirOpClzN 4.50 4.52 Butyryl 94 108-109 CloH11OLClnK 5.76 5.65 66 126-127 CldIlsOtClzN 4.48 4.32 Valeryl 94 86-87 Cl1H1302Cl& 5.54 5.34 99 149-160 C17H1702ClzN 4.11 4.14 4.14 5.34 C17Hl702C12N 4.11 Isovaleryl C ~ ~ H ~ I O ~ C ~5.38 ZN 83 123-124 93 94-90 3.98 Caproyl 5.10 5.07 C1BH1802C12N 4.03 CI?Hl&CLN 98 101-102 59 136-137 4.83 ClQHplO2Cl2i\j 4.00 3.83 Enanthyl C13H1702ClzN 4.83 97 98-99 37 107-108 Nitrogen analyses by semi-micro Dumas method. Amide and anilide reported: C. A. Bischoff, Ber., 34, 1837 (1901); Amide and anilide reported: C. A. Bischoff, ibid., ibid., 34, 1839 (1901), m.p. 132-133' and 118.5-119", respectively. 34, 1837 (1901) and ibid., 34, 1840 (1901), m.p. 123' and 93-94", respectively. Propionyl
In an effort to study the i d u e n c e of different alkyl radicals upon the properties and character of alkylphenoxy disubstituted ketenic substances, these studies were extended to several a-ohenoxv and a(1) C M Hill, C, W Senter .ind M. R. Hill, T k J o o ~ v ~72, ~ r2286 ,
< 1950)
an acid chloride apparently influences the extent and mode of polymerization of the disubstituted ketenes formed upon dehydrohalogenation with tri ethvlamine. DehYdrohalogenation Of propionyl and chlorides of the a-phenoxy series produced two iso-
PHENOXY SUBSTITUTED ACIDCHLORIDES
April, 1951
1661
meric ketene dimers only. One monomer and one dimer were obtained from each of the other acid chlorides of this series. In the 2,4-dichlorophenoxy series, all acid chlorides except propionyl and enanthyl produced one monomer and two isomeric dimers. Formation of the isomeric dimers is indicated by the equation 2R-CH-CO-Cl
EtsN __f
While no attempt was made to determine the configuration of these isomeric ketene dimers, i t is believed that, on the basis bf the ryclobutanedione
b *
'28 DJ DJ DJ
E
g
P%%q@ Z %%% M m m m
"-?
Lm m? v g . p +
g.2 >e
1662
CARL
PHYSICAL
Phenoxy, ketenes
iMethyl dimers Ethyl dimer5 Propyl monomer dimer
11.H I L L , HELENI. SCHOFIELD, ALFREDs. SPRIGGS AND
CONSTANTS ASD ANALYTICALDATA B.p., Yield, ‘C. Mm. % ’
i
150-152 182-184 135-137 175-178
n-Butyl monomer dimer %-Pentyl monomer dimer
E. HILL
VOl. 73
TABLE IV PHENOXY-SWBSTITUTED KETENE MONOMERS AND DIMERS
FOR
MRD
Found
dM4
Calcd.
1.5303
Analyses Mol. wt. Carbon. % Hydrogen, % FoundCalcd. Found Calcd. Found Calcd.
Formula
2 10 1.5309 2 69 1.1818 1.5361 78.11 79.23 Ci8H16O4 2 33 1.1191 1.5165 87.52 88 47 2 43 1.1541 1.5285 86.51 88 37 C20H2a04
110-112 10 10 226-229 6 74 M.p. 108-109
XfARY
{ 291 297
296 296 326 324 325 324
i
72.35 72.61 73.67 74.01
72.97 72.97 74.04 74.04
5.80 5.45 6.35 6.30
5.41 5.41 6.17 6.17
172 176 75.11 75.00 6.87 6.82 354 352 75.15 75.00 6.97 6.82
CiiHizOz C22H~404
113-115 3 18 1,0044 1.4982 54.47 55.20 CijH1402 205-209 3 72 C2rH2sOd M.P. 65-66
181 190 75.10 75.79 7.40 7.37 384 380 75.50 75.79 7.35 7.37
8 38 1.0186 1.4953 58.44 59.82 CisHibOz C2&0( 6 46 1.5055
202 204 76.20 76.47 7.50 7.84 351 408 76.35 76.47 7.67 7.84
135-138 210-214
2,4*Dichloro-
phenoxy ketenes
Methyl monomer dimer
68-70 2 9 1.2706 1.5489 54.32 49.83 CoHsGClr 215 217 49.48 49.77 3.00 2.77 168-170 2 36 ClaH1tOdCl4 427 434 49.60 49.77 2.90 2.77 M.p. 110-111
Ethyl monomer
130-133
clitners
Propyl monomer dimers Isopropyl monomer dimers
4 16 1.3140 1.5380 54.99 M 15 CloHaOnCls
180-183 8 41 M.p. 92-93 M.p, 103-104 30
138-140
2 3 3 6 M.p. 110-111 66
f 190-192
1
C?oHieOiClr
1,5074 1.5381
110-114 3 7 175-177 2 5X * M.p. 82.j 9.) [ 83.5
dimers Pentyi monomer dimer
112-115 2 I O 180-185 3 14 M.P. 87-88 42
4 I396 462 51.79 51.95 3.67 3.46
CiiHinOzC12 242 245 53.79 53.88 4.27 4.10 483 490 53.84 53.88 4.35 4.10 492 490 53.75 53.88 4.06 4.10 CIiHioOrCl? 238 245 53.69 53.88 4 17 4.10 :487 490 53 70 53 88 4 32 4 10 CizHio04Cl* ‘ 4 1 6 190 53 80 53.88 4 38 4.10
I-
Butyl monomer
230 231 51.70 51.95 3.60 3.46 1427 462 51.81 51.95 3.35 3.46
1 . 5230 1,5169
174-17(i :; I i M.P. 93-94 25
ethanol. Addition of the ethanol precipitated the hydrazide which was purified by recrystallimtion. Data describing the phenylhydrazides are given in Table 111. Phenyl Esters.-To a 1.0-g.sample of the chloride was added an equivalent amount of pure phenol. The mixture was refluxed for three hours over a hot-plate. The crude product was washed with water, dried over anhydrous calcium chloride and distilled under reduced pressure. The phenyl esters are described in Table 111. Ethyl Esters.-A 1.0-g. sample of each ehloride was dissolved in 20ml. of 95% ethanol and refluxed for one hour over a water-bath. The excess ethanol was removed by distillation; the crude ester washed d t h water, dried over anhydrous calcium chloride and distilled under reduced pressure. Physical constants and analytical d a t a of the esters are shown in Table 111. Dehydmhalogenation.-A dilute diethyl ether solution of each acid chloride was dehydrohalogenated by treatment
C12H1202C12 256 259 55.47 55.60 4.70 4.63
{ 502
518 55.10 55.60 4.52 4.63
C!4H~40aC14 514 518 55.39 55.60 4.57 4.63
ClsHlrOzClz 270 273 57.09 57.15 4.87 5.02 CLoH>s04Cl( 502 546 57.70 57.15 5.01 5.02 with an equimolar amount of triethylamine in a manner similar to that previously reported In no case was unreacted acid chloride recovered. When dehydrohalogenation of the chloride produced two forms of the dimeric ketene, it was found that a fairly satisfactory separation could be made by taking advantage of solubility differences. The procedure which proved most effective was as follows: The diethyl ether solution of the ketenic suhstances was concentrated, a small portion of dry petroleum ether added and the solution chilled. The mixture was filtered, thus separating one form of the dimeric ketene. This procedure was repeated several times. F W l y , the residue was distilled under reduced pressure from a modified Claisen flask to isolate the second form of the dimeric ketene. Physical constants and analytical data for the ketenic substances are shown in Table I V . NASHVILLE, TENXESEE
RECEIVED AUGUST24,1950
