Steric influence on the reactivity of amino radical ions. New type of benzylic chlorination

Tetrahedron LettersNo.7, pp, 699-700,1966, PergamouPreraLtd. Printedin GreatBritain,

BPPlIC IBFLUEUCIa W

EADICAL I=&

PIICTIVITTOFAMIHO

IIRTTPE C#BBZILIC CELOBIYATI~. hulOO8oo ninini,luo aalli ud Iwmna

lemudi.

18titutolliakirioa do1 Politoonieo,mlauo. (Beceived 20 December 1965) =TLY

w.'hava

~omtalrtd

br protomato&I-ohloruminom l ttaak uomstio riy

A #rag

that th, amino rdiod

am& roduoiag

irm,~onoratd

wtal ultm,mSmltuoawly

sub baasyllo podtieam of the dkylbonsonom.

dorio offoothaa boon lboorvod la the lrtho pooitlono in

nuc1oor -ion. Horo wo report that thou

two oolpotltivo roaotiemo are otrem&

l ffootod bP the atorloarturo of the alkyl grmpm im I-ohloroamimom.

Eemltm with mrersl r;jioldo am

I-ohlorouiao# and toluoao arm liotod in toblo rad have bean

baood on Sohlorouiaoo

dotorminod br

gacllquld ohroaoto&rophy. Foblo 1

bonql

S-ohloro~et~lamino milphateand Fe* I

”

ohlorido 24

and Tl++ md Fo

16

I-&ilorodiethylamino n

51

24

II-ohlorodi-n-butTlamb

*

14

n

2l%

Sohloropiperidln~

a

q

II-ohlorodliaobutylamiae q

26

All the rorotionahrvo boon oarriod out under tho oomo oonditiono, ot room temperature(20-2o*C)In 20 mlnutw,by adding oolld forrorlo oolphoto or

titmopm ohlorido to the mirturo of I-ohloroomin.,

699

NO.7

7QQ

toluao,nlghorio

and

cm. inorrdybulk

aoetio

aold

(ratio

6/l).

of the ~l&roupm

a doorus. of nuolou

atkak

and u

iaI-ohlorouin.m dotormlna~

lnoroamo of

bonsylloablerinrtion,

whiah im uoluml~ with Sohlaodllsobut~lamin~ md I-ohloredl-a-butylmane. Ii&

ofbbnsyl

ahloridmim

low with Sohlorodl-n-butrlamino owl-

to the oarpotltionwith intruolooulu rrotion (EofWm-tiff1.r ro&ian) . Alao .

orgotltf~

rodnotion

of the amine radioal slway8 oooma

to mm. lxtoat: r$++i +

r.++ .-

Ppl

&kn~lodgomont~.Wo rimh to thak Rofomor ~mtionti

and dimowmiez~m.

+

Ir.-

A.Quilloo

for helpful