The Synthesis, Properties and Dehydrohalogenation of Some α

The new constants do not alter any of our qualitative arguments. Acknowledgment.—We are indebted to Drs. F. Lipmann and K. Laki for a number of very...
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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