A. P. KOLACIK AND E. EMMET REID
“3i
TABLE111 EFFECTOF PALLADIUM ON TKE DECOMPOSITION OF I B m n HYDROPEROXIDE Time, min. 0 10 23 52 0.01982 N thio, cc. 66 0 38.0 22.0 21.7 The results in Table 111 seem to indicate that palladium black slowly accelerates the decomposition of l-butyl hydroperoxide in a dilute solution of disodium phosphate. However, pure l-butyl hydroperoxide is only slowly attacked by palladium black and a pure sample of it stirred over this catalyst for several months was still qtronglv peroxidic.
summary
I.
t-Butyl hydroperoxide has been prepared
[CONTRIBUTION FROM THE CHEMISTRY
Vol. 60
by the fractionation of an anhydrous solution of hydrogen peroxide in t-butyl alcohol in the presence of dehydrating agents. 2. This peroxide has been found to be very stable under ordinary conditions. 3. Pure liver catalase and horse-radish peroxidase have very little or no effect on the decomposition of t-butyl hydroperoxide. 4. Palladium black catalyzes slowly the decomposition of t-butyl hydroperoxide in dilute solution of disodium phosphate, although the tfecomposition of the peroxide is only slightly affected by this catalyst. RECEIVEDJULY 2, 1938
CAMRRIDGE. I V A N
LABORATORY OF JOHNS HOPKINS UNIVERSITY 1
Lengthening Carbon Chains by Three Units: Assay of primary Bromides from the Addition of Hydrogen Bromide BY A. P. KOZACIK AND E. EMMET KEID I t is well known that an alkyl bromide may be converted into a primary alcohol with either O I K or two additional carbon atoms in the chain. The object of this investigation was to provide a method of lengthening a carbon chain by three -CHz- units : RBr ----f RMgBr -+ RCH,CH= CH2 -+ RCHsCH2CH2Br. This combines an old reaction with one’ that has been studied only recently. In addition to lengthening the chain this gives odd-numbered bromides from the readily obtainable even. I t was particularly interesting to extend these reactions to the higher alkyls and to aromatics. Another object was to identify the primary bromides by crystalline derivatives and to get a rough estimate of their purity. The abnormal addition of hydrogen bromide is of great theoretical interest; the availability of the primary bromides so produced for syntheses is
a practical question of importance. The alkenes are given in Table I. The addition of the hydrogen bromide was carried out by Professor Kharasch.2 Our results show conclusively that the primary bromides are obtained. The melting points of these are in Table 11. I t was too much to expect that the technique which he has developed for the lower alkenes would apply to the higher without some modification. Unfortunately the whole amounts of the alkenes that were available were run through with the standard technique before any of the products were tested. The results were good with nonene-1 but very poor for heptadecene-1 and nonadecene-1. The identity of the synthetic bromides was shown and their approximate purity estimated by their reaction with para substituted phenols. For compari-
TABLE I PROPERTIES OF Alkence
n-C11HpCH4H* n-Ci,HnCH=CHa ~-CI$I,ICHE=CHI ~-CITH*CHICHI GHr(CHi)rCH=CHr CdHr( CHs),CH=CHr
Press.. M...., mm.
B. p., ‘C. 10!2-103 10 127.5-128.5 10 155.4-156.4 10 10 177 181-182 757 94.5-95 10
-13 2.8 11.2 21.:
-
ALKENES
a, 0.7858 .7921 .7892*, .7881)m,
(1) Kharnrch and co-workers, T A IJOURNAL. ~ 66, 2469, 2621 nnd 2531 (1933).
THE
d.4
0.7070 ,7751 ,7859 .71WPr
IWD
1.4328 1.4363 1.4417
(2) M. S . Kharascb and W m . (1937).
Bromine no. Wcd. Found
62.8 55.7 49.7 46.9
03.0 63.7 54.6 64.6 47.7 48.5 46.7
Yield,
%
77 07
43 56 77 87
M. Potts, J . &e. C k m . . 1.
196
LENGTHENING CARBONCHAINS BY THREE UNITS
Oct., 1938
From n-undecyl bromides
son the authentic bromides previously prepared* were treated with the same phenols, under the same conditions and usually a t the same time. The products were crystallized two or more times. The phenyl derivatives were treated with @-naphthol. Only in the case of 3-phenylpropyl bromide was an authentic sample available for comparison. TABLE I1 MELTINQPOINTS OF AUTHENTIC(A) AND SYNTHETIC (S) BROMIDESAS RECEIVED Carbons
A
S
Diff.
Minimum estimated purity
12
82 65
9
11 13 15 17 19
-13.15 5.94 18.63 28.40 38
-25 -15 7.4-8.4 1-2 13-15
21 10
26 23
41 60 12 3
From the results in Table I11 it will be seen that the products from the synthetic bromides axe somewhat less in amount and melt lower than those from the authentic. The losses on the first crystallization are even more significant. Taking the data for the nonyl bromides, we find this loss to average 11% for the authentic and 28 for the synthetic. In the second crysta,Uization the losses were nearly the same. For practical purposes the primary bromide present may be estimated by comparing the final yields of the twice crystallized derivatives with those from the authentic bromides. These estimates may be regarded as minimum values. Thus we can say that there was a t least 82Q/, of the primary bromide, and probably somewhat more, present in the synthetic nonyl bromide. The other syn-
2437
CiHirO
Crude 1st cr. 2nd cr. CIOHIIO Crude 1st cr. 2nd cr. ClzHaO Crude 1st cr. 2nd cr.
99 81 75 93 76 71 76 60 59
67 45 41 83 51 46 73 43 36
18
7
33 9
18 7
38 10
21 2
41 16
69-60 69-60 60.4 66-68 68-69.5 69.8 66-69 71-71.5 71.8
62-56 58-59 60.6 57-62 67-68 69.8 58-63 70-70.5 71.8
57-60 61-62 62.8 62-63 64-64.5 64.8 67-68 67.5-68 67.6
55-59 60-61.5 62.8 55-60 64-65 65.2 58-63 67-67.5 67.5
From n-tridecyl bromides
CIHoO
Crude 1st cr. 2nd cr. 6 H ~ 0 Crude 1st cr. 2nd cr. C1oH:lO Crude 1st cr. 2nd ET.
92 82 70 95 78 73 90 79 72
69 29 27 67 32 30 75 25 23
11 15
58 7
18
52
6
6
12
67 8
8
From n-pentadecyl bromides ClrEIniO
c1
I
Crude 1st cr. 2nd cr. Crude 1st cr. 2nd cr. Crude 1st cr. 2nd cr.
92 73 67 95 76 67 89 65 57
a3 54 40 71 34 19 77 37 33
8
35 26
20 12
52 44
27 12
52 11
21
73-74 74-75 75.0 44-47 46-47 48.0 53-55 56-57 57.2
6.'
72-74 74.2 39-44 4445.5 47.2 45-50 55-56.5 57.0
From n-heptadecyl bromides
PhCHaO
c1
I
Crude 1st er. 2nd cr. 3rd cr. Crude 1st cr. 2nd cr. Crude 1st cr. 2nd cr.
89
67
70
..
8 97 27 86 3 8 1 . . 96 44 82 10 78 6
88 91.2 91.8
,.
11 6
89
15 5
77 40
50-52 53-54 54.2 60-61 62-62.5 64.0
80-84 84-88
89.8 91.6 45 52-53 53.8 67-59 61-62 63.4
From n-nonadecyl bromides H
Crude Istcr. 2ndcr.
98 73 69
8 4 2
25 5
50
50
51-55 56-56 56.0
47-51 47-51 56.0
TABLE IV FROM AUTAENTICAND SYNTHETIC PHENYLDERIVATIVES FROM AUTHENTICAND SYNTHETIC BROMIDES DERIVATIVES ALKYL BROMIDES AND @-NAPHTHOL AND #-SUBSTITUTED PHENOLS, #-XC~HIOH,YIELDSAND Loss on MELTINGPOINTS OF CRUDE AND CRYSTALLIZED Yields, recrystallization Melting points, 'C.
TABLE I11
Loss on recrystallizaYields, % tion, % Melting points, 'C. A S A S A S X From n-nonyl bromides clg,,O Crude 87 81 58-58 1st cr 78 60 10 26 58-59.5 54-55 60.0 2 n d ~ . 73 56 6 7 60.0 57-89 CIOHO~,IO Crude 85 84 62-63 1st u. 78 62 8 26 62.6-63 62-62.5 63.4 8 7 63.8 2ndcr. 72 58 C I S W Crude 86 88 6 2 4 3 . 5 65-59 1st w. 76 61 12 a1 64-64.6 63-64.6 2pd tr. . 67 7 65.2 64.8 80-83 CirHaO * b d e 86 86 64-66 65-66 1st Q. 76 64 12 26 65-66 66-66 2 n d ~ . 73 80 4 6 67.4
(a)
Meye? and R d d , TEISJoux~yar, 60, 1577 (1933).
A
3
A
S
A
S
From phenyl-propyl bromides
1st cr. 2nd cr.
63 47 43
Crude 1st cr. 2nd a.
.. .. ..
Crude
..
Crude
59 44 38
25
9
25 14
66-67 62-64 69-69.5 68.5-69 69.&70 69.0-69.5
From phenyl-butyl bromide
48 32 26
38 19
47-53 64-55 64.5-55.5
From phenyl-hexyl bromide
1st Q. 2nd cr.
.. ..
31 18 15
42 17
63-77 78-78.5 78.5-79
RUSSELLE. MARKER AND ELMER J. LAWSON
2438
thetic bromides do not show up so well: the undecyl may be estimated to contain a t least GFjT, of the primary, the tridecyl, 41, the pentadecyl 60, the heptadecyl 13 and the noiiadecyl otily 3 . The melting points of the bromides put them i l l the same order as to purity.
Experimental
the derivative to separate as a granular solid which wa.s collected on a filter and washed twice with water. The product was crystallized twice or thrice from alcohol. For better comparison the derivatives of the authentic and synthetic bromides were prepared at the same time with the same reagents and the crystallizations were carried ou side by side. The final melting points were kindly Laken by Mrs. Carrie Gutman Moses with a standardized t hcmianc.ter.
The procedure of Gilman' for the preparation of thc Griguard reagents was followed. These reagents were used according t o the method of Wilkinson,6 for making the alkenes, which were separated from the disproportionation by-products of the Grignard reaction, heated with sodium and distilled. The properties of the new alkenes are to br found in Table I. The bromine numbers were determined by the method of Francis' as modified by Cortese.' Preparation of Derivatives.-To prepare a derivative, 0.3 to 0.5 cc. of the alkyl halide was measured into a test tube with 3 cc. of alcohol and about 10% excess of the phenol. As CloHtsBr is a solid, it was weighed. This mixture was heated to effect solution and a slight excess of 1 N alcoholic potash added. The test-tubc was stoppered loosely and placed with others in a beaker of water kept at about 70" for about twelve hours. At the end of the heating any alcohol that had evaporated was replaced and 2 cc. of hot water added. Thc mixture was boiled for a moment and then cooled quickly with violent slinking. This caused (4) Gilman. Zoellner and Ilickcy, THISJ O U R N A L , 51, 1570 (lW29). ( 5 ) Wilkinson, J . Chenr. S n c . 120, 3057 (1931). (6) Francis, I n d . Eng. Chevi..18, S21 (1920). ( 7 ) Cortesr Rec. ii'iiim c i i i ~, 48, i I i 4 fI!I2'1 i
( ' ( I N 1 K I W I J I ION I?RO\I THE W t l O O l O F CtIEMISI H\
Sterols. XLIV.
VOl. 60
For preparing derivatives para substituted phenols were used. Experience in another investigation had shown that these give derivatives that are readily purified and iiielt a t convenient temperatures. The monoalkyl hydroquinone ethers will be described later along with other dcrivativrs made from them.
summary I . h method has been devised for transforming an alkyl bromide into another alkyl bromide having a carbon chain longer by three units. 3. A method has been worked out for assaying the mixture of bromides obtained by the addition of hydrobromic acid to unsaturates. 3. By the preparation of known crystalline derivatives the formation of primary bromides by the addition of hydrobromic acid to alpha alkenes in the presence of peroxides has been confirmed. I ~ A I . T I M O R R , Mn.
A N D PLXYSICS OF
RECEIVED JULY 1, 1938
TREPENNSYLVANIA STATE
Ci>Ll,P,GR
I
Pregnanone-3 and Related Compounds*
Bs RUSSELLE. MARKERA N D ELMERJ - LAWSON
Although all the pregnanediols, pregnanolones. and pregnaeediones isomeric about CB,Ca and GOhave been described,' none of the correspond itig pregnanols and pregnanones are kticwt I . Since we now have indications of the occurrence it1 urines of pregnane derivatives having otily 0111' oxygen atom,2 we have begun the synthesis of ctjmpounds of t h i s type for purposes of comparison and physiological testing. The present paper describes the preparation of pregnanoite-:( atirl the isomeric 3-pregnanols. Pregnanol-3(a)-one-20 was reduced by the Clemmensen method with amalgamated zinc and a mixture of acetic and concentrated hydrochloric acids. The reaction mixture, carried (*) Paper XLIII, THISJOURNAL, 60, 1904 (1938). (1) Market, Kamrn. Wittle, Oakwood. Lnuson nnd T aucitis. TATS J O U ~ N A L 69,2291 , (1937). (2) Tlnpiiblished r u u l t s
from This Laborarnrr
through the acid succinate separation, yielded only 19 mg. of pregnanol3(a), but about 250 mg. (m. p. 102') of what proved to be pregnanol-3 acetate could be crystallized from the non-hy. droxylated fraction, and a further crop of preg.iiatiol-3(a) was obtained from the mother liquor after alkaline hydrolysis and acid succinate separation. 'The lion-hydroxylated fraction, amounting to about 20% of the reaction mixture, did iiot yield any crystalline products. Since it was thought at first that the crystalline product might be a pregnene, which could be identified by ozonolysis to give 31 14 pregnane-3,4diacidI3or an isomer, this acid was prepared by the Clemmensen reduction of 20-keto-3114pregnane-3,4-dia~id.~The latter forms a 2,4(3) This nomenclature is suggested by Sobotka, "Chemistry of t h r Wterids." Williams and Wilkins, Baltimore. Md., 1938, p. 163. 45 Nutaoandt. ~ n OS, . , 859 (inao): 64, a m ( 1 ~ 1 ) .
