[CONTRIBUTION FROM THE DEPARTMENT

OF CHEMISTRY, THEUNIVERSITY OF TEXAS]

SYXTHESES INVOLVING UTILIZATIOK OF ALLYLMAGNESIUM

BROMIDE Ih’ THE GRIGNARD REACTIOK
HENRY R. HENZE, BRUCE B. ALLE?;,f AND WILLIAM B. LESLIE

Received April 6, 19@

Prior to 1928 the use of allyl bromide in the Grignard reaction required a pro-
cedure other than the usual one of independently preparing the alkylmagnesium
reagent and then introducing the substance to which addition is desired. The
method which actually had been used when the allyl group was to be utilized,
involved the simultaneous mixing of allyl halide, anhydrous ether, the ‘compound
with which reaction was desired, and magnesium. This “batch” method
(Barbier-Grignard procedure) had seemed necessary in view of the fact that
previous attempts to form allylmagnesium bromide as such had resulted for
the most part in the production of diallyl (1,2),2 caused by interaction of the
allylmagnesium compound and excess allyl bromide.
CH2=CHCH2Br +
Mg -+CHFCHCH2MgBr
+
CHFCHCH2MgBr CH?CHCH2Br + CH2=CHCH2CH2CH=CH2
nfgBr2 +
However, in 1928, Gilman and McGlumphy (4) not only brought about the
initial synthesis of allylmagnesium bromide, but also outlined a method for its
preparation whereby a yield of eighty to ninety per cent of the theoretical
might be expected in ordinary synthetic procedure. The method, as described,
requires the use of a large excess of magnesium (three equivalents), a high dilu-
tion with anhydrous ether, vigorous stirring, and slow addition of the bromide;
such factors allowing minimum contact of allyl bromide with the allylmagnesium
bromide during formation of the latter. As an indication of the increased
yields to be had through use of the preformed reagent, rather than of the afore-
mentioned “batch” method, the amounts of products obtained by Gilman and
McGlumphy in three typical reactions are tabulated. For purposes of com-
parison, yields of these products as previously prepared from the same reactants
but by the “batch” method are included in Table I.
Subsequent to the pioneering work of Gilman, several investigators have
made rather detailed studies of various factors which determine the optimum
yield of allylmagnesium bromide and the results of these studies confirm Gilman’s
initial findings. Thus, Johnson and Adkins (8), testing the effect of copper
upon the yields of Grignard reagents, found that allyl bromide reacts with
copper-magnesium alloy to form only a six per cent yield of the reagent; using
magnesium in essentially Gilman’s proportion, however, they were able to
obtain seventy-two per cent of the theoretical yield of allylmagnesium bromide.
1 Present address: Tubize-Chatillon Co., Rome, Ga.
2 Houben, Boedler, and Fischer (3) have shown t h a t a t best only twenty-five per cent
of the theoretical yield of the allylmagnesium reagent may be obtained from the usual
proportions of reactants.
326
 SYNTHESES WITH ALLYLMAGNESIUM BROMIDE 327

Young, Prater, and Winstein (9), in an effort to determine the effect of solvent
upon yields of crotyl- and allyl-magnesium bromides, found that for the latter
the usual diethyl ether served more adequately than did ethers of higher molec-
ular weight. In a study of the relative usefulness of RMgCl versus RMgBr,
Zoellner (10) concluded that for most purposes the chloride is to be preferred to
the bromide, but in the case of the allylmagnesium halide reagent the chloride is
unsatisfactory, becoming colloidal and useless in the majority of instances, and
recommended the bromide for routine synthesis.
In view of Gilman’s work and of the wide application of the Grignard reaction
in synthetic organic chemistry, it is surprising indeed to note the infrequency
of use of allylmagnesium bromide. Apparently, the reagent has found its
chief use in reactions of the type
R-halide + CH2=CHCH2MgBr -+ RCH2CH=CH2 + MgBrz
+ Mg (halide)z
Shoemaker and Boord (11) have satisfactorily employed the reagent in an exten-
sive study of the 1,4-diolefins, as have Summerbell and Bauer (12) in the

TABLE I
COMPARISON FROM ALLYL BROMIDE
OF YIELDSOBTAINED IN THE GRIGNARD
SYNTHESIS

Product
1 Percentage yields obtained using

I I

1 1
RMgBr “Batch”

Allyldiphenylcarbinol. ................................... 74.9@(4,5) 60 (6)

All ylmethylphenylcarbinol ............................... 80.2 (4) 60 (6)
Butenoic acid. .......................................... 21.7 (4) 11 (7)

~ In a repetition of the synthesis of this carbinol, Kharasch and Weinhouse (5) essentially
duplicated this yield in obtaining 72%.

preparation of 2,3-diallyl-l,4-dioxane from 2,3-dichloro-l,4-dioxane. In this

connection, however, Kogerman (13) was unable to bring about reaction between
allylmagnesium bromide and vinyl bromide in an effort to synthesize
1,4-pentadiene.
Recently (14), in this Laboratory, we attempted to prepare an alkoxyalkyl
allyl ketone by interaction of ethoxyacetonitrile and allylmagnesium bromide.
Instead of the anticipated ketone, however, the product of the reaction was
shown to be diallylethoxymethylcarbinamine. The same type of reaction
occurred between allylmagnesium bromide and the methoxy- and isopropoxy-
analogs. In view of this unexpected behavior of allylmagnesium bromide, and
“2

ROCH2CN + 2CHz=CHCH2MgBr -
(HoHL I
ROCHz CCH2 CH=CHz
I
CHz CH=CH2
because of the paucity of records of its use, it was desirable to study the reaction
of the reagent, as prepared by Gilman (4), with a few common aldehydes,
328 HENZE, ALLEN, AND LESLIE

ketones, esters, unsaturated aldehydes, and ketones, and then with a few com-
pounds containing both carbonyl and ether groupings.
I n this investigation, allylmagnesium bromide reacted with the following:
propionaldehyde, n-butyraldehyde, n-valeraldehyde, acetone, ethyl methyl
ketone, isobutyl methyl ketone, acrolein, crotonaldehyde, mesityl oxide, ethyl
propionate, propyl ethoxyacetate, 1-methoxyethyl methyl ketone. Of these,
all save the valeraldehyde and the two alkoxy derivatives, had previously been
converted into the corresponding allyl carbinols, chiefly by the “batch” method
with utilization of either zinc or magnesium. I n general, the yields here reported
equal or exceed those recorded elsewhere.

EXPERIMENTAL

The allyl reagent was prepared using a ratio of three equivalents of magnesium to one of
allyl bromide and nine volumes of anhydrous ethyl ether. After six to seven hours of vigor-
ous stirring a t room temperature, the mixture was warmed for thirty minutes and then
transferred rapidly into another flask by decantation through a coarse filter to remove the
unreacted metal.3 Slightly less than one equivalent (0.25 mole) of the appropriate car-
bonyl compound was diluted with an equal volume of dry ether and added to the chilled
reagent. I n some cases the addition product separated as a light gray solid, in others as
an amber oil, but in a few instances remained in solution. The addition product was de-
composed by action of crushed ice and chilled, dilute hydrochloric acid. After the usual
procedure of ether extraction, washing and drying, the carbinols were fractionated for
purification.
5-Hexen-3-oZ. From 14.5 g. (0.25 mole) of propionaldehyde was obtai,ned 15.6 g. (62%
yield) of material boiling a t 129-136’, but when purified by fractionation under 753 mm.
boiling at 131.5-132.0’ (corr.); 56-55’ (33 mm.). The purified alcohol, a colorless liquid of
penetrating, disagreeable odor, amounted to 13.2 g. (52% yield); n: 1.4320; d? 0.8409;
7 2 0 24.70 dynes/cm; M E calc’d 30.97; found 30.89; P calc’d 277.2; P found 265.4. A
comparison of certain of these data with those previously reported in the literature follows:

TABLE I1
PHYSICAL
CONSTANTS,
5-HEXEN-3-OL
Mol. Refract.
Boiling Range Yield, %
Calc’d I Found

130-132’”
128-133’’’ 760-765 mm. 48 0.843
d 2 i 0.8464
I1 1.4330
d 2 i 0.8409 1I 1.4320

Fournier (15) used a [‘batch” method with zinc and allyl bromide.
(1

bLevene and Haller (16) used essentially and same method as in ( d ) .

e Ou, K.-H. (17) used allylmagnesium bromide.

d This study.

3 It was found to be more efficient to prepare the Grignard reagent in a flask with a glass
tube attached off-center to the bottom. This tube was fitted with a stopcock and could be
filled with a fine-mesh copper screen or glass wool as a filtering medium. The ether solution
could this be transferred to another flask without exposure to the atmosphere.
 SYNTHESES WITH ALLYLMAGNESIUM BROMIDE 329

I-Hepten-4-ol. Utilization of 36.0 g. (0.5 mole) of n-butyraldehyde yielded 37.7 g. (66%)

of material boiling a t 152.5-154.8" (743 mm.). Upon redistillation the carbinol boiled a t
66" (20 mm.); 151.7-152.2" (corr.) (743 mm.); 57% yield; n: 1.4342; d"," 0.8374; yZo 25.43
dynes/cm.; ME calc'd 35.58; M R found 35.51; P calc'd 316.2; P found 306.2.
Anal. Calc'd for C,H1PO: C, 73.63; H, 12.36.
Found: C, 73.36; H, 12.62.
I-Octen-4-ol. This compound, which had not been reported previously, was prepared
from 43 g. (0.50 mole) of n-valeraldehyde. Upon first distillation of the product there was
collected 53.8 g. (84% yield) of liquid boiling a t 6669" (10 mm.); upon redistillation the

TABLE I11
PHYSICAL CONSTANTS, l-HEPTEN-4-OL

-
145-146" a
Boiling Range Yield, %

I
1 *' I
j
Mol. Refract.

Calc'd I Found
_______

59-60" ~ 35 dz2,l 0.8384 n18 1.4345 35.58 k35.501

149.5-150.2"~ $0 0.8412 n201.4355 35.58 35.44
660d 20 mm. 66 d*O 0.8374 nZo1.4342 35.58 35.51

a Knorr (18) used a modified batch method in which some allyl chloride reacted with a
large excess of magnesium; then were added allyl bromide, benzene, ether, and the aldehyde.
b Consden, Duveen, and Kenyon (19) reported "Considerable difficulty was experienced
in the preparation of this alcohol." Addition of aldehyde to allylmagnesium chloride gave
poor yields and much high-boiling material. Hence, an ether solution of allyl chloride and
n-butyraldehyde was added very slowly to a well-stirred suspension of magnesium in ether.
"On one occasion the yield was as high as 65%, but was generally only about half this
amount. The crude alcohol, b.p. 58-59' (18 mm.), contained a variable amount of n-
butanol. "
c Karasev (20) used allylmagnesium bromide.

d This study.

alcohol (65% yield) boiled a t 68-69" (10 mm.); 171.5-172.0" (corr.) (748 mm.); n: 1.4383;
d: 0.8373; y*o 26.00 dynes/cm.; M R calc'd 40.22; M E found 40.20; P calc'd 355.2; P found
345.7.
Anal. Calc'd for C8HleO: C, 74.94; H, 12.58.
Found: C, 74.67; H, 12.66.
a-Methyl-4-penten-2-02. Twenty-six and eighth-tenths gram (70% yield) of this carbinol
was obtained, from 22 g. (0.38 mole) of acetone, when collected a t 115-117'. Upon redis-
tillation, 20.3 g. (53% yield) boiled a t 118.0-118.2" (corr.) (744.5 mm.); 46.0-46.5' (30 mm.);
n: 1.4263; d y 0.8298; y20 24.12 dynes/ dm.; M R calc'd 30.97; M E found 30.94; P calc'd 277 .2;
P found 267.5.
Anal. Calc'd for CeHI20: C, 71.95; H, 12.08.
Found: C, 71.68; H, 12.30.
b-MethyZ-6-hesen-8-02. By use of 18 g. (0.25 mole) of ethyl methyl ketone, 24.2 g. (84%
yield) of product, boiling a t 137-139", was obtained. The purified alcohol boiled a t 138.0-
138.5' (corr.) (742 mm.); 60.5-61.0" (35 mm.); 1.4370; n? 1.4342; d? 0.8442; d2: 0.8403;
y 24.42 dynes/cm.; M E calc'd 35.58; M R found 35.44; P calc'd 316.2; P found 300.7.

: 73.63; H. 12.36.
Anal. Calc'd for C ~ H U O C,
Found: C, 73.74; H, 12.51.
330 HENZE, ALLEN, AND LESLIE

4,6-DimethyZ-i-hepten-4-01. Fifty-nine grams (83% yield) was obtained from 50.1 g.

(0.50 mole) of isobutyl methyl ketone, the latter having been prepared by catalytic hydro-
genation of mesityl oxide using the Adams catalyst. The alcohol was collected a t 75'

TABLE I V
PHYSICAL CONSTANTS, 2-METHYL-4-PENTEN-2-OL
Mol. Refract.
Boiling Range Yield, % d'
Calc'd Found

119.5" (corr.)a d'," 0.8307

120" (atm. press.) b
118.3-118.8"C8
d
75
118.5-119.5°g 39
3236" (12 mm.) 60-65 d': 0.8326 nlr 1.4277 30.97 30.90
117-119" (775 mm.)f
120"g d': 0.8270 nzo 1.4120 30.97 30.77
46.0-46.5' (30 mm.) 70
118.0-118.2" (744.5 mm.) * 53 d2: 0.8298 nZo 1.4263 30.97 30.94

0 Saytzeff and Saytzeff (21) used a "batch" mixture of zinc, allyl iodide and acetone.
b Court,ot (22) used same procedure as in h.
c Jaworsky (23) dropped an ether solution of allyl chloride (or bromide) and acetone onto

magnesium and obtained a 52% yield of material boiling a t 115-125'.

Jaworsky (24).
e Jaworsky (6) used allyl bromide in "batch" method.

f Bacon and Farmer (25) used allylmagnesium bromide.

g Ou, K.-H. (17) used allylmagnesium bromide.

h This study.

!
Mol. Refract.
Boiling Range Yield, % dt !n
Calc'd 1 Found

138.5-139.5' (753 mrn.). d': 0.8421

138-139" (atm. press.) 52 d*! 0.8365 1.4309 35.58 35.33
138.0-138.5' (742 mm.)c 85 da: 0.8442 1.4370 35.58 35.44

a Saytzeff (26) used zinc and allyl iodide.

b Milas and McAlevy (27) used allylmagnesium chloride.
c This study.

(26 mm.), b.p. 188.3-168.8" (corr.) (757.5 mm.); n; 1.4402; dy 0.8380;7 2 0 25.16 dynes/cm.;
h l calc'd
~ 44.82; M E found 44.76; P calc'd 394.2; P found 380.1.
Anal. Calc'd for C9Hl80: C, 75.99; H, 12.75.
Found: C, 75.75; H, 12.80.
1,6-Hexadien-5-oZ. Fourteen grams (0.25 mole) of acrolein yielded 16.3 g. (66%) of
crude product boiling a t 126-136" (746 mm.); fractionation gave 14.4 g. (58.7% yield) of
 S Y N T H E S E S WITH A L L Y L M A G S E S I U M BROXIDE 331

alcohol distilling at 133.6-134.0"(corr.) (754 mm.); 60.5-61.6"(40 mm.); nt 1.4471;d;

0.8608;yZ0 25.08dynes/cm.; MR calc'd 30.50;IllR found 30.46;P calc'd 266.2;P found
255.1.
Anal. Calc'd for CsHl00: C, 73.43;H, 10.27.
Found: C , 73.27;H , 10.42.
1,6-Heptadien-Q-o1. This carbinol was obtained in 82y0 yield (23.2g.) from 17.5g. (0.25
mole) of crotonaldehyde, the crude material being collected a t 72-75' (32.5mm.). When

TABLE VI
PHYSICAL CONSTANTS,4,6-DIMETHYL-l-HEPTEN&OL

Mol. Refract.
Boiling Range Yield, % dt n4,
Calc'd Found
- ______
173.7"(corr.) (765mm.). 15.5 d 2 i 0.8355
180-182" (753mm.)b d21 0.823 n18 1.4443 44.82 [45.931
68-49' (20 mrn.). 60
168.3-168.8'(747.5mm.)d 83 d2: 0.8380 nz0 1.4402 44.82 44.76
-

TABLE VI1
PHYSICAL CONSTANTS, 1,5-HEXADIEN-3-OL

Boiling Range 1 Yield, %

Mol. Refract.

Calc'd I Found

133-134"(atm. press.)" d26 0.8596 n25 1.4464 30.50 1 30.47

130-137"
130-131O C About d20 0.8578 n20 1.445 30.50 30.34
50
133.5-134.0'(754mm.)d 58.7 d20 0.8608 n20 1.4471 30.50 30.46
1' Levene and Haller (30)used zinc and allyl bromide, but reported "It can also be pre-
pared by the action of acrolein on allyl magnesium bromide," and calc'd: C, 73.43;H , 10.20;
found: C, 73.95;N , 10.39.
* Butz, Butz, and Gaddis (31)used allylmagnesium bromide. They reported the crude
alcohol to boil a t 45-65" (25mm.) and calculated the yield as 74-7974 (based on the acrolein
used, and 4144% based on the bromide). If the theoretical amount of acrolein was used,
the yield was 3540% (based on acrolein) while twice the quantity gave about 20%. About
90% of the product boiled 130-137"or 42-48' (17mm.).
Ou, K.-H. (17)used allylmagnesium bromide.
,i This study.

fractionated a t 15 mm., the alcohol boiled a t 62.0-62.5'(corr.); 155-156" (742mm.); n:

1.4533;d? 0.8590;y z o25.48 dynes/cm.; M R calc'd 35.12;M R found 35.32;P calc'd 305.2;
P found 293.3.
.4,6-Dimethyl-l,6-heptadien-4-01. Sixty-three and eight-tenths grams (91% yield) of
this compound, boiling a t 169.7-170.2'(corr.) (750mm.), was produced from utilization of
332 HENZE, ALLEN, AND LESLIE

49 g. (0.50 mole) of mesityl oxide; b.p. 4748" (4 mm.); 72" (18 mm.); n: 1.4598; d? 0.8622;
yZo26.31 dynes/cm.; Mg calc'd 44.35; Mg found 44.53; P calc'd 384.2; P found 368.7.

Anal. Calc'd for CeHleO: C, 77.09; H, 11.50.

Found: C, 76.85; H, 11.33.
2,4-Dirnethylheptan-4-01.This alcohol was obtained through reduction :
A . Thirty and one-half grams (0.215 mole) of 4,6-dimethyl-l-hepten-4-01
was dissolved
in an equal volume of absolute ethanol, mixed with 0.34 g. of the Adams catalyst' and

TABLE VI11
PHYSICAL CONSTANTS, 1 5-HEPTADIEN-4-OL
] Mol. Refract.
Boiling Range Yield, R d' 1 .'
Calc'd Found

68-90" (24 mm.) 16.5 d'"' 0.8668 n':' 1.4553 35.12 35.07
156.0-156.7' dec. (765 mm.)O
61-62' (15 mm.) d': 0.8612 ~ ng 1.4541 35.12 36.26
54-55' (6 rnm.)O 49
59" (15 mm.)d d19J0.8599 n'L6 1.4556 35.12 35.41
150-151 50 d2: 0.8598 n': 1.4523 35.12 35.13
68.C-68.2" (24 mm.)' 50 dzo 0.8633
82.0-62.5" (15 mm.)g 82.8 d2: 0.8590 n*: 1.4533

5 Enklaar (32) used allyl bromide and zinc in a batch mixture.

bAuwers and Westermann (33) used allyl bromide and zinc in batch mixture.
e Icnorr (18).

d Duveen and Kenyon (34) used allyl chloride and magnesium in a batch mixture.
e Ou, K.-H. (17) used allylmagnesium bromide.
Pel'kis and Pazenko (35) used allyl bromide and magnesium in a batch mixture.
p This study.

TABLE IX
PHYSICAL CONSTANTS, 4'6-DIMETHYL-1, 5-HEPTADIEN-4-OL

Boiling Range Yield, % d' n:,

~ _ _ _ _
168-170" (760 mm.)"
71" (20 mm.)b 4 I d";'0.8652 1.4583
~ 2 ~ 8 . 7 44.35 44.24
58' (2 mm.).
72" (18 mm.)d
~
75
91 I dz1 0.8701
de: 0.8622 nzo 1.4598 44.35 1 44.15
44.53
 SYSTHESES WITH ALLYLMAGKESIUM BROMIDE 333

B . From 38.5 g. (0.275 mole) of 4,6-dimethyl-1,5-heptadien-4-01 in the presence of 0.5

g. of the Adams catalyst with hydrogen under 2@ lbs./sq. in., reduction was slow and in-
complete; the catalyst was shown not t o be poisoned and was extremely reactive in reduction
of other substances, under these conditions of temperature and pressure. However, this
mixture hydrogenated readily when shaken a t 60" for ninety minutes with hydrogen under
900 lbs./sq. in.
I-Methozyethyl methyl ketone. This ketone, needed in the synthesis of the following
carbinol, was prepared by interaction of the appropriate Grignard reagent, produced from
8 g. (0.33 gram atom) of magnesium and 39 g. (0.28mole) of methyl iodide, and 22.1 g.
(0.26mole) of a-methoxypropionitrile (39). The yield was 12 g. (45%) of 1-methoxyethyl
methyl ketone (40)boiling a t 114.0-114.5" (corr.) (745 mm.); n t 1.3968; d? 0.9063; .ME
calc'd 26.94;M E found 27.13.

TABLE X
PHYSICAL CONSTANTS, 2,4-DIMETHYLHEPTAN-4-OL

Mol. Refract.
Boiling Range n:,
~ d2:
Calc'd Found

170-171" (750 mm.)5 d20 0.826 n18 1.4318 45.29 [45.29]

75" (19 mm.)b d i : 0.8230 n20 1.4292 45.29 [45.08]
A 171.3-171.8"c(756mm.) d 2 i 0.8254 1.4298 45.29 45.13
B 171.2-172.2OC(751 mm.)
-
1 dz: 0.8261
I
n20

n20 1.4304 I 45.29 45.14

a Bodroux (29). The carbinol was prepared by the Grignard reaction, utilizing n-
propylmagnesium iodide and isobutyl methyl ketone.
ti Meyer and Tuot (38)likewise used the Grignard reaction.
c This study.

TABLE XI
PHYSICAL CONSTANTS, 4-ETHYL-I,
6-HEPTADIEN-4-OL
-
Boiling Range I Yield, % 1 dt I fi2:
" I Mol. Refract.

Calc'd Found
-
175-176' (743.5mm.) ' d l i 0.8637
175-176" (755.6 mm.) 39 d2: 0.8688
176.5-177.0"(750 mrn.). 73 dZ: 0.8685 1.4587 44.35 44.11
334 HENZE, ALLEN, AND LESLIE

lection of the fraction at 172-174'. Upon redistillation, the ester boiled at 173.5" (corr.)
(748 rqm.); n; 1.4083; d? 0.9594; 7 2 0 28:34 dynes/cm.; M E calc'd 37.82; M E found 37.62;
P calc'd 356.2; P found 351.4.
Q-Ethoxymethyl-l,6-heptadien-.4-oZ.The above ester (30 g. or 0.21 mole) was added t o
the Grignard reagent prepared from interaction of 50 g. (2.06 gram atoms) of magnesium
and 80 g. (0.66 mole) of allyl bromide; the yield was 32.3 g. (90%) of tertiary alcohol boiling
a t 105.0-106.5" (36 mm.). Upon redistillation a t 15 mm., the material boiled a t 86-87',
198.0-198.5' (corr.) (744.3 mm.); n; 1.4500; d'," 0.9025; 72026.07 dynes/cm.; M R calc'd 50.61;
M R found 50.69; P calc'd 442.2; P found 426.2.
Anal. Calc'd for C10H~802:C, 70.55; H, 10.66.
Found: C, 70.49; H, 10.75.
4-Ethyl-l , 6-heptadien-4-ol. One-fourth mole (25.5 9 . ) of ethyl propionate yielded 23.4
g. (66%) of material boiling a t 81.5-86.0' (30 mm.); redistillation yielded the purified al-
cohol, b.p. 82-84" (32 mm.); 176.5-177.0' (corr.) (750 mm.); n: 1.4587; d: 0.8685; yZo26.21
dynes/cm.; M E calc'd 44.35; M E found 44.11; P calc'd 383.2; P found 364.8.

SUMMARY

Allylmagnesium bromide has been utilized in the Grignard reaction with

representative saturated and unsaturated aldehydes and ketones, and alkoxy
ketones and esters. A comparison of yields obtained in this study with those
obtained in "batch" procedures, involving allyl halides, a carbonyl compound
and zinc or magnesium, is unfavorable to the latter (and older) method.
AUSTIN, TEXAS.
REFERENCES
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(2) CORTESE,J. Am. Chem. SOC.,61, 2266 (1929).
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(4) GILMANAND MCGLUMPHY, Bull. SOC. chim., [4] 43, 1322 (1928).
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(18) KNORR, German Patent 544,388, Frdl., 18, 180 (1933).
(19) CONSDEN, DUVEEN, AND KENYON, J . Chem. SOC.,1938, 2104.
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