ALLYL CHLORIDE

1

Allyl Chloride

1

Cl

[107-05-1]

C

3

H

5

Cl

(MW 76.53)

InChI = 1/C3H5Cl/c1-2-3-4/h2H,1,3H2
InChIKey = OSDWBNJEKMUWAV-UHFFFAOYAQ

(allylating agent which attacks C, O, N, S, Se, Te nucleophiles;
organometallic derivatives provide homoallyl alcohols; expected

electrophilic addition reactions)

Physical Data:

mp −136.4

◦

C; bp 44.6

◦

C; d 0.938 g mL

−1

.

Solubility:

miscible with organic liquids.

Form Supplied in:

colorless liquid, discoloring on standing and

exposure to air.

Purification:

wash with concd HCl, then with aq Na

2

CO

3

and

dry (CaCl

2

). Impurities include isomers and chloropropanes;

efficient fractional distillation is essential.

2a

Handling, Storage, and Precautions:

volatile, flammable, toxic,

irritant, alkylating agent.

Usually manufactured by high temperature chlorination of

propene;

2b

hence the incidence of isomeric and polychlorinated

impurities. Allyl chloride allylates ethyl acetoacetate derivatives
(40% aq KOH, Bu

4

NBr, rt, 3 h) to give 2,2-diallyl analogs (92%

yield, 97% pure).

3

Malonic esters are similarly alkylated under

dehydrating conditions (RCl, Bu

4

NBr, NaOH in PhMe).

4

Alkyl

carboxylic acids may be allylated at the α-position when the Na
salt (NaH–xylene, 135

◦

C, 2 h) is treated with Lithium Diethyl-

amide at 125–135

◦

C until loss of Et

2

NH is complete, followed

by treatment with RCl at ∼85

◦

C over some hours.

5

Ruthenium

or osmium σ-acetylide complexes (e.g. 1)

6

undergo allylation (at

the alkyne system). Some such substitutions (e.g. methanolysis)
are apparently Cu catalyzed;

7,8

an example is the formation of

3-allylpentane-2,4-dione (72%), when Cu + Cu(ClO

4

)

2

is added

to the reagents in Et

2

O (eq 1).

8

Cl

O

O

O

O

+

(1)

O

O

O

O

R

Ru(C≡CR)(PPh

3

)

2

(η-C

5

H

5

)

(1)

(2)

In the presence of peroxides (e.g. 1,1-Di-tert-butyl Peroxide)

crown ethers add to allyl chloride via the α-hydrogen abstracted
radical to form, for example, 2-(3

′

-chloropropyl)-1,4,7,10-

tetraoxacyclododecane (2; R = Cl(CH

2

)

3

). While the yields are

poor (8–10%) the product is apparently isolable,

9

and affords a

route to functionalized crown ethers.

The reductive allylation process (eq 2) occurs with aldehydes

in the presence of Bi,

10a,10b

Al/BiCl

3

,

10b,10c

Al/PbBr

2

,

11

Zn,

12

and Fe/BiCl

3

.

10b

Acid chlorides in the presence of Cp

2

Sm af-

ford allyl ketones.

13

Dry stirring Magnesium turnings in an inert

atmosphere greatly promotes the formation of allylmagnesium
chloride without the formation of biallyl and similar products.

14

In addition to the expected range of Grignard reactions based upon
allylmagnesium chloride, allyl chloride reacts with Lithium Di-
isopropylamide to form α-chloroallyllithium, which undergoes
the expected reactions with RCl, RCHO, R

3

SiCl, and R

3

SnCl

(eq 3).

15

Cl

(2)

R

R′

OH

+

RCOR′

R = H, alkyl
M = Zn, Fe, Al, etc.

M

H

H

Cl

H

H

Cl

(3)

H

H

Cl

LDA

R

R = alkyl, R

3

Si, R

3

Sn

Allyllithium (RLi) itself is made by cleavage of RSnPh

3

(from RBr, Mg, and Ph

3

SnCl)

16a,16b

or of allyl aryl ethers

(Li, THF, −15

◦

C) (eq 4).

16c

H

H

SnR

3

H

H

Li

(4)

Li

The protected glycine ester derivative (3a) affords a reagent

with 2LiCl·CuCN which allylates with allyl chloride to give the
product (3b) without loss of the stereochemical identity at the car-
bon atom α to the protected amino group (eq 5).

17

Allyl chloride

also alkylates glycine chiral ester Schiff bases in the presence of
chiral Pd complexes.

18

The allylation of the monomenthyl ester

of cyclopentane-1,2-dicarboxylic acid by RCl (R = allyl) gives
the compound (4) in which the allyl halide has approached from
the more hindered side of the molecule. Allyl tosylate gives the
sterically preferred orientation; the differences in behavior are ra-
tionalized in terms of interaction between the Li of the enolate
reagent and the Cl of RCl.

19

IZn

NHBoc

CO

2

Bn

Cl

CO

2

Bn

NHBoc

(3a)

(3b)

(5)

2LiCl

·

CuCN

HO

2

C

R

O

i

-Pr

O

(4)

Avoid Skin Contact with All Reagents

2

ALLYL CHLORIDE

Traditional nucleophilic attack is represented by reaction with

ArO

−

in the synthesis of allyl aryl ethers in a study of the Claisen

reaction,

20

and with Sodium Sulfide to give R

2

S,

21

and in the

analogous preparation of R

2

Te.

22

Friedel–Crafts allylation of ben-

zene represents an alternative route to the synthesis of propyl-
benzene after hydrogenation, since rearrangement occurs when
propyl halides are subject to this reaction; hydrated Iron(III)
Chloride proved to be a gentle, if inefficient, catalyst for such
allylations.

23

The use of Ru or Rh chlorides on polyethylenimine

to promote the addition of CXCl

3

to unsaturated systems such

as allyl chloride (eq 6) extends the older application of Lewis
acids such as Aluminum Chloride.

24

The addition of Diborane to

allyl chloride provides (γ-chloropropyl)boranes which then
provide cyclopropane;

25a

with Sodium Amide, allyl chloride gives

cyclopropene (low yield).

25b

(6)

Cl

Cl

Cl

XCl

2

C

CXCl

3

+

Related Reagents. Allyl Bromide; Allyl Iodide.

1.

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2.

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3.

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4.

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6.

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7.

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11.

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14.

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15.

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16.

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21.

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Roger Bolton

University of Surrey, Guildford, UK

A list of General Abbreviations appears on the front Endpapers