Polyamine-Chelated Alkali Metal Compounds

2 Synthetic Aspects of Tertiary Diamine Organolithium Complexes W. NOVIS SMITH Downloaded by IMPERIAL COLL LONDON on June 7, 2014 | http://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/ba-1974-0130.ch002

Foote Mineral Co., Exton, Pa.

19341

The metalations of benzene, toluene, propene, and 1-butene with butyllithium-TMEDA complexes were studied. Factors controlling the metalation rate are discussed including temperature, structure of butyllithium isomer, amount of TMEDA, and solvent. Optimum conditions are described for the formation of TMEDA complexes of benzyl-, phenyl-, allyl-, and crotyllithium and benzyllithium · triethylenediamine (TED). Synthetic uses of these complexes demonstrate that they react in the same way as other organolithium compounds. Ring-isomer formation during metalation of toluene using n-butyllithium-TMEDA complexes is also examined. The conditions for the lithiation of TMEDA and other tertiary diamines and monoamines (including trimethylamine) are given. The reaction of lithiated TMEDA with 1-bromobutane produced N-n-pentyl-N,N',N'-trimethylenediamine in 40% yield.

TT he l i t e r a t u r e d e s c r i b i n g t e r t i a r y d i a m i n e o r g a n o l i t h i u m c o m p o u n d s has g r o w n t r e m e n d o u s l y since the i n i t i a l announcements of these versatile reagents (1, 2). M u c h of this literature has centered o n p o l y m e r i z a t i o n or p o l y m e r studies u s i n g these complexes as catalysts. T h e synthetic p o t e n t i a l of these complexes a n d t h e i r preparations h a v e b e e n discussed, b u t there has b e e n no intensive s t u d y to d e t e r m i n e the o p t i m u m c o n d i t i o n s for t h e i r p r e p a r a t i o n for synthetic a p p l i c a t i o n s (1-6). S y n t h e t i c a p p l i c a t i o n s u s u a l l y r e q u i r e a n i s o l a t i o n step or some p r o c e d u r e to ensure p u r i t y of the complex. E v e n investigations of the g e n e r a l u t i l i t y a n d c o n d i t i o n s for use of these complexes are not extensive. T h e most significant factor i n t h e i r r e a c t i v i t y f r o m a synthetic p o i n t of v i e w is the a b i l i t y of these complexes to metalate or r e p l a c e c e r t a i n a c t i v a t e d h y d r o gens i n h y d r o c a r b o n s w i t h the l i t h i u m c a t i o n (7, 8). T h e n e w a r o m a t i c ,

/

,

A

23

In Polyamine-Chelated Alkali Metal Compounds; Langer, A.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

24

P O L Y A M I N E - C H E L A T E D A L K A L I M E T A L COMPOUNDS

b e n z y l i c , or a l l y l i c o r g a n o l i t h i u m t e r t i a r y d i a m i n e c o m p l e x

is t h e n r e

a c t i v e e n o u g h to react selectively w i t h a v a r i e t y of reagents: >N ~

Ν < . # L i + # ' H -> RR +

>N ~

Ν < -JÎ'Li

(1)

T h e results r e p o r t e d here describe a n i n v e s t i g a t i o n of the o p t i m u m c o n d i t i o n s of p r e p a r a t i o n of t h e t e r t i a r y d i a m i n e p h e n y l h t h i u m , b e n z y l l i t h i u m , a l l y l l i t h i u m , a n d l i t h i a t e d T M E D A complexes.

These

reagents

w e r e a l l o w e d to react w i t h some c o m m o n reagents to h e l p d e l i n e a t e the

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s y n t h e t i c usefulness of the complexes. T h e a c c o m p a n y i n g papers i n this v o l u m e , the l i t e r a t u r e c i t e d i n t h e m , a n d this p a p e r discuss reasons for the e n h a n c e d r e a c t i v i t y of these c o m plexes.

M e c h a n i s t i c discussion has b e e n left to a m i n i m u m i n this p a p e r

to e m p h a s i z e p r e p a r a t i v e a n d synthetic aspects.

( A u s e f u l a n a l o g y as to

w h a t these complexes c a n d o or h o w t h e y w i l l react is to consider t h e i r b e h a v i o r to b e s i m i l a r to h y d r o c a r b o n soluble a l k y l s o d i u m c o m p o u n d s i f t h e y w e r e to exist. ) Results and

Discussion

Reactivity

of Various Tertiary Diamines

in the Preparation of Previous

Tertiary Diamine Organolithium Complexes by Metalation.

w o r k has s h o w n that the r e a c t i v i t y a n d the rate of m e t a l a t i o n for R e a c t i o n 2 of the t e r t i a r y d i a m i n e o r g a n o l i t h i u m complexes is a f u n c t i o n of the t e r t i a r y d i a m i n e i n the c o m p l e x (1,9). R RLi

^ R i

3

·

~

+ ^ R

R4 R—Η

+

Aromatic Benzylic Allylic

2

I n the specific case of the m e t a l a Aromatic Benzylic Allylic

) > —C—Li )

·

R3>. J^N R 4

) \— C — H ) ~

-»

Ri NC" ^ R

(2)

2

t i o n of b e n z e n e as s h o w n i n R e a c t i o n 3, a t e r t i a r y d i a m i n e w a s a d d e d to n - b u t y l l i t h i u m i n b e n z e n e at r o o m t e m p e r a t u r e i n a 1:1

molar ratio.

A f t e r the i n i t i a l t e m p e r a t u r e rise, the h e a t e d s o l u t i o n b e g a n

evolving

η-butane at 4 5 ° - 5 0 ° C (η-butane is v e r y soluble i n benzene, a n d u s u a l l y

„.B

u t e

»e

+

g * ?

·

(0f

U


(3)

2.

SMITH

25

Tertiary Diamine Organolithium Complexes

no gas e v o l u t i o n occurs unless the t e m p e r a t u r e is r a i s e d ). T h e rate of gas e v o l u t i o n was q u i t e sensitive to t h e structure of the t e r t i a r y d i a m i n e . T h e o r d e r of r e a c i v i t y o b s e r v e d tetramethylethylenediamine butanediamine >

u s i n g this p r o c e d u r e

was

Ν,Ν,Ν',Ν'-

( T M E D A ) > N,N,N^'-tetramethyl-l,3-

N^^^N'-tetramethyl-l^-propanediamine >

triethyl-

e n e d i a m i n e ( T E D or D A B C O ) a n d 2 - m e t h y l t r i e t h y l e n e d i a m i n e > N^N'-tetramethyl-l^-butanediamine. tetramethylmethylenediamine

T h e tertiary diamines,

N,N 9

Ν,Ν,Ν',Ν'-

a n d N , N ' - d i m e t h y l - l , 4 - p i p e r a z i n e , caused

l i t t l e or no gas e v o l u t i o n i n d i c a t i n g essentially no m e t a l a t i o n i n the h o u r


i n w h i c h the other t e r t i a r y d i a m i n e complexes reacted. T h e o r d e r of r e a c t i v i t y agrees w i t h p r e v i o u s s t u d i e s — T M E D A b e i n g by

f a r the most

reactive

of

the r e a d i l y a v a i l a b l e t e r t i a r y d i a m i n e s .

[ S p a r t e i n e appears to be the most a c t i v a t i n g of the t e r t i a r y d i a m i n e s investigated ( I , 1 0 ) ] . increased

R e c e n t reports b y L a n g e r a n d others i n d i c a t e t h a t

a c t i v a t i o n is e x p e c t e d f r o m the m e t h y l t e r t i a r y

polyamines

c o n t a i n i n g m o r e t h a n t w o b a s i c nitrogens, a l l separated b y t w o (II).

P r e p a r a t i v e a n d synthetic w o r k c e n t e r e d o n T M E D A

carbons

and T E D

( D A B C O ) because of t h e i r e c o n o m i c p r a c t i c a l i t y . Optimum Conditions for Preparing Phenyllithium from

Benzene.

T h e o p t i m u m p r o c e d u r e for m e t a l a t i o n of a n a r o m a t i c c o m p o u n d i n h i g h y i e l d w a s to use the a r o m a t i c c o m p o u n d itself as the solvent.

The alkyl

l i t h i u m c o m p o u n d u s e d m a i n l y i n this s t u d y was n - b u t y l l i t h i u m because it w a s c o n v e n i e n t a n d e c o n o m i c a l . T h e following general procedure

was u s e d to d e t e r m i n e t h e

com

p l e t i o n of r e a c t i o n . T h e c a l c u l a t e d a m o u n t of T M E D A was a d d e d to the s o l u t i o n of n - b u t y l l i t h i u m i n b e n z e n e o v e r one stirred solution

(under

argon)

to t w o

was k e p t at the d e s i r e d

minutes.

The

temperature;

a l i q u o t s of this r e a c t i n g solution a n d the final s o l u t i o n w e r e t h e n t a k e n , a l l o w e d to react w i t h t r i m e t h y l s i l y l c h l o r i d e , a n d a n a l y z e d b y G L C . T h e s e results m a y i n d i c a t e the m e c h a n i s m of the m e t a l a t i o n r e a c t i o n i n a d d i t i o n to d e t e r m i n i n g o p t i m u m

metalation conditions

for

benzene.

T h e results are l i s t e d i n T a b l e I. A n u m b e r of conclusions c a n be d r a w n . T h e effect of excess t e r t i a r y d i a m i n e a b o v e a 1-mole e q u i v a l e n t is not as significant for r a p i d m e t a l a t i o n as is the i n i t i a l a m o u n t of T M E D A .

Practical metalation could only

be o b t a i n e d w i t h a 1:1 m o l a r ratio at 4 0 ° C a n d a 2:1 r a t i o at 6 0 ° C ; the 4:1 r a t i o r e q u i r e d reflux.

S i d e reactions a p p e a r e d to cause a p r o b l e m

o n l y w i t h the 4:1

r a t i o at the h i g h e r temperatures.

Benzene

solvent a c c e l e r a t e d

the r e a c t i o n s i x f o l d over hexane

with 10%

excess as the solvent.

as

the mole

S o m e of this acceleration m a y be solvent effect.

T h e use of s e c - b u t y l l i t h i u m i n c r e a s e d the m e t a l a t i o n rate eight times. A s expected, the m e t a l a t i o n rate i n c r e a s e d w i t h temperature.

The

rate w a s r e l a t i v e l y r a p i d over the i n i t i a l 6 0 % a n d t h e n s l o w e d d r a m a t i -


26

POLYAMINE-CHELATED ALKALI M E T A L

Table I.

Run


1

Study of the Metalation Rate of Benzene by Butyllithium and T M E D A

Molar Ratio BuLi: TMEDA

T, °c

1:1

22

e

2

2:1"

22

3

1:2"

22

4

1:1°

40

5

2:1 3

2

2

3

(CH ) N(CH ) N(CH )CH Li + 3

2

2

2

3

2

C H 4

(7)

1 0


I Since t h e n , f u r t h e r w o r k b y L a n g e r a n d his c o - w o r k e r s has s h o w n t h a t this is a g e n e r a l r e a c t i o n w i t h the h i g h e r h o m o l o g s of T M E D A

(5,

8).

P r e p a r a t i o n of these l i t h i a t e d t e r t i a r y d i a m i n e s a n d a n u m b e r of s y n t h e t i c reactions are g i v e n i n those references.

A s f u r t h e r b a c k g r o u n d to the

possible reactions that m a y o c c u r w i t h other t e r t i a r y amines a n d d i a m i n e s , the w o r k of L e p l e y a n d co-workers w i t h n - b u t y l l i t h i u m a n d a r o m a t i c tertiary amines s h o u l d also b e e x a m i n e d

(29-33).

O n e p r o b l e m i n w o r k i n g w i t h the l i t h i a t e d t e r t i a r y d i a m i n e s is that they w i l l u n d e r g o f u r t h e r d e c o m p o s i t i o n w h e n o v e r h e a t e d or o n s t a n d i n g . F o r example lithiated T M E D A yields lithium dimethylamide, d i m e t h y l v i n y l a m i n e , a n d l i t h i u m a c e t y l i d e ( J , 2, 5, 34).

Lithiated T M E D A

(I)

i n hexane decomposes at a rate of 0 . 5 2 % of the i n i t i a l l y c o n t a i n e d m a t e r i a l p e r d a y at 3 5 ° C . T h e r e f o r e solutions of the l i t h i a t e d t e r t i a r y d i a m i n e s a n d amines s h o u l d b e stored at 1 0 ° C or l o w e r for l o n g p e r i o d s of storage. T h e p r e p a r a t i o n of m o n o l i t h i a t e d N ^ N ^ A ^ - t e t r a m e t h y l e t h y l e n e d i amine (I)

was s t u d i e d u n d e r several sets of c o n d i t i o n s to o p t i m i z e its

preparation.

T h e l i t h i a t i o n of other t e r t i a r y m o n o a m i n e s

and diamines

w a s also e x a m i n e d . T M E D A was a d d e d i n 1:1 m o l e ratios to h y d r o c a r b o n solutions of the a l k y l l i t h i u m c o m p o u n d .

T h e solutions w e r e k e p t at a g i v e n t e m p e r a -

t u r e u n t i l gas e v o l u t i o n ceased.

T h e d a r k , o r a n g e - b r o w n solutions w e r e

a n a l y z e d u s i n g the G i l m a n p r o c e d u r e

w h e n complete

r e a c t i o n of

the

and C r o t y l l i t h i u m - T M E D A Product

Product mp or bp, °C

1, l - d i p h e n y l - 3 - b u t e n - l - o l 1-ally Icy clohexanol 2 , 3 - d i m e t h y l - 4 - p e n t e n - 2 - o l , a n d trans2-methyl-4-hexen-2-ol

a

%

125 (0.6 m m ) 64 (7.5 m m ) 6 5 - 7 1 (120 m m )


Yield 91 52 11

42


s t a r t i n g a l k y l l i t h i u m was o b s e r v e d bound

(17).

l i t h i u m gave r e p r o d u c i b l e ,

T h i s analysis for the

consistent

results for

carbon-

the l i t h i a t e d

tertiary diamines. However

inconsistencies

w e r e f o u n d i n this p r o c e d u r e

tions of l i t h i a t e d t e r t i a r y m o n o a m i n e s

w i t h solu

so that o n l y t o t a l base titrations

w e r e u s e d for t h e i r analysis. I n most cases a s m a l l a m o u n t of the d e c o m p o s i t i o n p r o d u c t was

filtered

f r o m the p r o d u c t solution.

h y d r o l y s i s p r o d u c e d d i m e t h y l a m i n e a n d acetylene

T h e solid on Product solu

(34).

tions u p to 30 w t % i n hexane w e r e r e a d i l y p r o d u c e d w i t h o u t s o l u b i l i t y


problems. served.

N o l i t h i a t i o n of T M E D A o n the m e t h y l e n e carbons w a s

T h i s was

determined

by

p r e p a r a t i o n of

the

ob

dimethylsulfate

d e r i v a t i v e of the l i t h i a t e d T M E D A a n d e x a m i n i n g for Ν,Ν,Ν',Ν'-tetramethyl-l,2-propanediamine

i n the

presence

of

the

product,

2V-ethyl-

N,N^N'-Wmethyl-l,2-ethanediamine. A l t h o u g h n - b u t y l l i t h i u m l i t h i a t e d the T M E D A efficiently at a c o n v e n i e n t rate, s e c - b u t y l l i t h i u m w o r k e d e v e n m o r e smoothly. terf-butyllithium caused

by

Surprisingly

was q u i t e p o o r , a l t h o u g h some of the p r o b l e m

t h e l o w - b o i l i n g solvent, pentane.

l i t h i u m i n r e f l u x i n g pentane

F o r instance

took 14 hours to c o m p l e t e l y

was

terf-butylreact

with

TMEDA. A s u m m a r y of the l i t h i a t i o n of t e r t i a r y amines a n d d i a m i n e s is g i v e n i n T a b l e X . T h e a c t u a l t o t a l base m i n u s the base s t e m m i n g f r o m c a r b o n b o u n d l i t h i u m present d i v i d e d b y the a m o u n t of c a r b o n - b o u n d present w a s u s e d to o b t a i n the r a t i o of t e r t i a r y n i t r o g e n to l i t h i u m r e p o r t e d i n the table.

Agreement between

lithium

carbon-bound

R u n s 1 t h r o u g h 11

w a s s u r p r i s i n g l y g o o d . Y i e l d s for the same runs w e r e also q u i t e g o o d — 90 to 1 0 0 % — w i t h b o t h n - or s e o b u t y l l i t h i u m . s e c - B u t y l l i t h i u m w a s p r e f e r r e d because of the m i l d e r conditions i n v o l v e d . T h e c o n d i t i o n s b e c o m e e s p e c i a l l y i m p o r t a n t w h e n l i t h i a t i o n of p o t e n t i a l l y m o r e sensitive more unreactive)

t e r t i a r y amines

or d i a m i n e s is a t t e m p t e d ;

(yet

Runs

9

t h r o u g h 15 s h o w some i n t e r e s t i n g b u t u n e x p l o i t e d m e t a l a t i o n results. T h e l i t h i a t i o n rate for the reactions i n T a b l e X w a s o b s e r v e d

by

gas

e v o l u t i o n , a n d the solutions w e r e a n a l y z e d w h e n the gas e v o l u t i o n ceased. R e a c t i o n o c c u r r e d i n o n l y a f e w hours w i t h s e c - b u t y l l i t h i u m a n d t r i m e t h y l a m i n e , b u t the y i e l d s s e e m e d to be l o w e r t h a n those o b t a i n e d with T M E D A . (CH ) N + 3

3

s e c - C H L i -> ( C H ) N C H L i + n - C H II 4

9

3

2

2

4

1 0

(8)

T h i s m a y be because I I has less t h e r m a l s t a b i l i t y t h a n does the l i t h i ated T M E D A

(I).

T h e l i t h i a t i o n of t r i m e t h y l a m i n e has also b e e n r e

p o r t e d u n d e r s l i g h t l y different c o n d i t i o n s b y Peterson ( 3 5 ) .

A n a l y s i s of


2.


SMITH

43

these t e r t i a r y m o n o a m i n e s i n R u n s 14 to 19 w e r e inconsistent u s i n g the G i l m a n d o u b l e t i t r a t i o n w i t h b e n z y l c h l o r i d e , a n d o n l y total-base t i t r a t i o n w a s u s e d for assay of the s o l u t i o n . It w a s a s s u m e d t h a t a l l d e c o m p o s i t i o n products,

including L i H and lithium dimethylamide, were

T h e l i t h i a t i o n of the t e r t i a r y m o n o a m i n e s

was p e r f o r m e d

insoluble.

i n a l l cases

w i t h a m o l e r a t i o of a l k y l l i t h i u m to t e r t i a r y m o n o a m i n e of 1:2 to k e e p the R L i : t e r t i a r y n i t r o g e n r a t i o the same as t h a t u s e d w i t h the t e r t i a r y d i a m i n e s . I n those cases n o t e d i n T a b l e X , the t o t a l base i n s o l u t i o n w a s m e a s u r e d a n d d i v i d e d b y three to estimate y i e l d .

(Analysis for

the


u n r e a c t e d s t a r t i n g a l k y l l i t h i u m was not affected i n these solutions. ) In

R u n s 10 a n d 12 the p r e c i p i t a t e w a s v e r y h e a v y a n d the t o t a l

s o l u b l e base was q u i t e l o w .

I n those t w o instances the p r o d u c t

was

a p p a r e n t l y i n s o l u b l e or the l i t h i a t e d t e r t i a r y a m i n e structure too u n s t a b l e and decomposition resulted. E a c h l i t h i a t e d t e r t i a r y a m i n e or d i a m i n e w i l l h a v e o p t i m u m c o n d i tions for p r e p a r a t i o n to ensure c o m p l e t e r e a c t i o n w i t h m i n i m u m d e c o m p o s i t i o n . T h e s e o p t i m u m conditions m a y b e d e t e r m i n e d b y o b s e r v i n g the rate of gas e v o l u t i o n as a f u n c t i o n of t e r t i a r y a m i n e or d i a m i n e r a t i o a n d t e m p e r a t u r e together w i t h analysis of the final s o l u t i o n o r slurry. O n l y a f e w reactions w e r e t r i e d w i t h the l i t h i a t e d t e r t i a r y amines a n d d i a m i n e s ; these are r e p o r t e d i n T a b l e X I . T h e y i e l d s f o r the c o u p l i n g of o r g a n i c h a l i d e s w i t h l i t h i a t e d T M E D A optimized reaction.

Changes

w h e t h e r some o b v i o u s

in a few

improvements

w e r e reasonable for a n o n -

conditions

were made

could be made.

y i e l d s r a n g e d f r o m 30 to almost 5 0 % .

to

see

I n general

the

A l k y l bromides

gave the best

y i e l d s i n this c o u p l i n g r e a c t i o n . T h e r e a c t i o n of l i t h i a t e d T M E D A w i t h a reactive ketone a n d a n a l d e h y d e a g a i n gave l o w y i e l d s .

(I) Less-

r e a c t i v e reagent molecules s h o u l d give h i g h e r y i e l d s . T h e l i t h i a t e d t r i methylamine

(II)

produced

a g o o d y i e l d of the a m i n e a l c o h o l

with

benzaldehyde, although l o w yields were obtained i n coupling w i t h

1-

i o d o p r o p a n e a n d 1-bromooctane. A n o t h e r possible p r o b l e m is i n the w o r k - u p of these since the p r o d u c t s are v e r y soluble i n w a t e r a n d organics.

compounds O n l y further

s t u d y c a n d e t e r m i n e w h e t h e r the p r o d u c t s f r o m the reactions of lithiated tertiary amine and diamine compounds

w i l l give

these

high-enough

p r o d u c t y i e l d s to p e r m i t these n o v e l o r g a n o l i t h i u m c o m p o u n d s to b e c o m e d e p e n d a b l e reagents for the chemist. Experimental A l l reagents w e r e r e a g e n t - g r a d e c h e m i c a l s . H y d r o c a r b o n solvents w e r e d r i e d over s o d i u m w i r e . T M E D A w a s d r i e d over s o d i u m w i r e a n d t h e n d i s t i l l e d u n d e r r e d u c e d pressure. T E D w a s t r i e d u n d e r v a c u u m to the p o i n t of s u b l i m a t i o n . L i q u i d t e r t i a r y amines a n d d i a m i n e s w e r e


44


Table X .

Time hr

RLi"

55 49

1.0 1.0

sec-BuLi sec-BuLi

3

47 55

1.25 1.0

sec-BuLi sec-BuLi

5 6

60 64

2.5 3.5

n-BuLi n-BuLi

36 45

14.0 0.75

iV,iV,iVW-Teramethyl1,3-butanediamine N,iV'-Dimethyl-l,4piperazine Triethylenediamine ( T E D )

55

0.75

feri-BuLi cyclopentyl Li sec-BuLi

65

1.0

sec-BuLi

65

1.0

sec-BuLi

63

1.5

sec-BuLi

13

iV,iV,iV',iV',-Tetramethylmethylenediamine iV-Methylpyrrolidine"

55

0.5

sec-BuLi

14

iV-Methylpiperidine"

55

1.5

sec-BuLi

15

Triethylamine"

65

1.0

sec-BuLi

16 17 18 19

Trimethylamine"

80* 70* 60* 60*

5.25 5.5 3.0 6.5

n-BuLi n-BuLi sec-BuLi sec-BuLi

Run 1 2"


Preparation of Lithiated

τ 8 9 10 11 12

Amine TMEDA

d

T°C

Hexane is solvent unless otherwise stated. Analysis done using total base and Gilman benzyl chloride coupling . Analysis of gas from hydrolysis of yellow ppt. snowed dimethylamine and acetyene present. Solvent is cyclohexane. R L i :tertiary diamine ratio is 1:2. a

b

(17)

c

d

e

a l l d i s t i l l e d before use a n d p r o t e c t e d f r o m air. A l l l i t h i u m c o m p o u n d s w e r e f r o m F o o t e M i n e r a l C o . E l e m e n t a l analyses w e r e p e r f o r m e d b y M i c r o - A n a l y s i s , Inc., of W i l m i n g t o n , D e l . A l l reactions w e r e r u n u n d e r a r g o n , a n d air-sensitive m a t e r i a l s w e r e also h a n d l e d u n d e r a r g o n . G L C analyses w e r e p e r f o r m e d o n a V a r i a n - A e r o g r a p h 9 0 P 3 C h r o m a t o g r a p h w i t h a t h e r m a l c o n d u c t i v i t y detector. T h e c o l u m n u s e d f o r t r i m e t h y l s i l y l d e r i v a t i v e s w a s 5-ft, S E - 3 0 / C h r o m a s o r b W .


2.

SMITH


45


Tertiary Amines and Diamines

Wt % Product Cone, in Sol.

Product Sol. Anal, t e r t N/RLi

% Yield

Comments

19.0 18.5

2.06 2.06

94 95

17.9

2.19

94

24.0 27.3

2.26 1.95

90 100

22.0 30.0

1.86 1.96

96 100

S l i g h t p p t . , no R L i left b y G L C Heated slightly beyond point w h e n gas e v o l u t i o n ceased. 2 % R L i left 5 % R L i left after 60 m i n at 55°C ; considerable p p t 5 % R L i left Heated slightly beyond point w h e n gas e v o l u t i o n ceased T r a c e R L i left, l o t of p p t 3 % R L i left, no p p t . , o n l y haze

21.4

1.86

95

12.3

2.20

68

7.6

/

0

h

b

3.1 (theory 3.0)

57

14.3

90*

14.4

98*

8.9

67*

6.6

60*

C

No

R L i left, some p p t . also formed N o R L i left, h e a v y p p t . ; d o u b l e t i t r a t i o n showed n o p r o d u c t N o R L i left, h e a v y p p t . ; a n a l y sis o n s l u r r y . N o R L i left, h e a v y p p t . ; d o u b l e t i t r a t i o n showed no p r o d u c t N o R L i left; heavy p p t

O n l y trace R L i left, m o d . p p t . ; d o u b l e t i t r a t i o n showed l o w yield. T r a c e R L i left, m o d . p p t . ; l o w low yield b y titration N o R L i left 5 % R L i left N o R L i left 8 % R L i left

Solvent is pentane. RLi:tertiary amine ratio is 1:2. Pressure reactor used.

Gilman double titration does not give good results with this amine; yield based on total base in solution. 1

«-Butyllithium in Benzene (or Toluene). A 12-liter flask e q u i p p e d w i t h stirrer, p r e s s u r e - e q u a l i z i n g d r o p p i n g f u n n e l , reflux condenser, a n d t h e r m o m e t e r was flushed t h o r o u g h l y w i t h a r g o n . ( N i t r o g e n m u s t not b e u s e d because it w i l l react w i t h l i t h i u m m e t a l p o w d e r . ) T h e flask w a s c h a r g e d w i t h 573 grams of 1 % N a - L i p o w d e r a n d 6,650 m l of benzene. T h e r e a c t i o n was first i n i t i a t e d w i t h 100 m l of 1-chlorobutane w h i l e stirr i n g . T h e t e m p e r a t u r e was m a i n t a i n e d at 3 5 ° - 3 7 ° C a n d the r e m a i n d e r


46


Table X I .

Run


1

Lithiated Compound* TMEDA

Reagent 1-iodobutane

Reactions of Lithiated

Addition T, °C

Total Time, min

- 5

30

0 10 68 0 -10

30 75 90 30 30

2 3 4 5 6

1-chlorobutane 1-bromobutane 2-bromobutane

7

iodobenzene

10

75

8

1-bromooctane

20

30

-20 -10 - 5

30 30 30

5

50

1-bromobutane

9 10 11

bromocyclohexane

12

cyclopentanone

13

valeraldehyde

-10

30

1-iodopropane 1-bromooctane valeraldehyde benzaldehyde

-10 -20 -10 -10

30 30 30 60

14 15 16 17

Trimethylamine

° Reagent added as a molar equiv. based on the lithiated T M E D A or trimethylamine present; solvent was hexane in all cases.

of t h e 3,310 grams of 1-chlorobutane was a d d e d over 3.5-hrs. T h e s l u r r y was s t i r r e d 2 h r m o r e before filtration. T h e y e l l o w filtrate a n a l y z e d to b e 2 6 . 9 9 % n - b u t y l l i t h i u m . T h e G i l m a n c o r r e c t i o n was 0 . 2 8 % ( 1 7 ) . T h e y i e l d was 8 3 % w i t h n o w a s h o n the filter cake. ( A c t u a l y i e l d e s t i m a t e d to b e a b o u t 9 0 % . ) Lithiation of Benzene by Λ - B u t y l l i t h i u m - T M E D A . A 5 0 0 - m l flask e q u i p p e d w i t h stirrer, reflux condenser, a n d t h e r m o m e t e r w a s p u r g e d w i t h a r g o n a n d t h e n c h a r g e d w i t h t h e r e q u i r e d a m o u n t of 2 4 . 4 % n - b u t y l l i t h i u m i n b e n z e n e (120 to 200 m l ) . T h e s t i r r e d s o l u t i o n w a s h e a t e d to t h e d e s i r e d t e m p e r a t u r e a n d the h e a t r e m o v e d . P u r i f i e d T M E D A w a s t h e n a d d e d i n the p r o p e r m o l a r r a t i o ( 30 to 50 m l ) u s i n g a large s y r i n g e over 0.5 to 1.0 m i n w h i l e c o o l i n g w i t h a h e p t a n e - d r y i c e b a t h to m a i n t a i n p r o p e r t e m p e r a t u r e . ( D o not use r a p i d a d d i t i o n f o r p r e p a r a t i o n s l a r g e r


2.

SMITH

47


T M E D A and Trimethylamine RLi Used for Lithiation of tert-Amine


sec-BuLi

n-BuLi sec-BuLi

Product

%

N-n-pentyl-N,N',N'-trïmethyl1,2-ethanediamine

iV-(2-methylbutyl)-iV,iV ,iV'. trimethyl-1,2-ethanediamine A^benzyl-A^A^N'-trimethyl1,2-ethanediamine iV-n-nonyl-iVjiV'jiV'-trimethyl1,2-ethanediamine ,

n-BuLi

sec-BuLi

n-BuLi

sec-BuLi n-BuLi

b

i V - ( c y c l o h e x y l m e t h y l ) -Ν,Ν', i V ' - t r i m e t h y l - l ,2-ethane diamine N- (hy d r o x y c y c l o p e n t y l m e t h y 1) i V ^ ' ^ ' - t r i m e t h y l - l ,2-ethane diamine iV-(2-hydroxyhexyl)-iV,iV^'trimethyl-1,2-ethanediamine iV,iV,iV-n-butyldimethylamine iV^jiV-n-nonyltrimethylamine condensation p r o d u c t iV,iV,iV-(l-hydroxyl-l-phenylethyl) dimethylamine

°C, bp

Yield

b

40

182

49 33 18 44 33

182 61 (4.5 m m )

30

69 (0.3 m m )

40

85 (0.5 m m )

37 30 18

69 (0.5 m m )

28

81 (1.5 m m )

39

84 (0.7 m m )

32 12

92 52 (2.9 m m )

49

72 (0.25 m m )

52 (2.9 m m )

See experimental for literature references and physical constants when available.

t h a n 250 m l — i t is too v i g o r o u s . ) T h e e v o l u t i o n of gas w a s o b s e r v e d as it passed o u t of t h e system t h r o u g h a n o i l b u b b l e r . P e r i o d i c a l l y a 2 - m l s a m p l e of t h e s o l u t i o n w a s w i t h d r a w n a n d i n j e c t e d i n t o a s e r u m b o t t l e c o n t a i n i n g 2 m l of t r i m e t h y s i l y l c h l o r i d e a n d 10 m l of d i e t h y l ether. T h i s d e r i v a t i v e s o l u t i o n w a s h y d r o l y z e d , w a s h e d , a n d d r i e d over a n h y d r o u s s o d i u m sulfate. T h e ether l a y e r w a s a n a l y z e d b y G L C , a n d t h e amounts of n - b u t y l t r i m e t h y l s i l a n e a n d p h e n y l t r i m e t h y l s i l a n e w e r e d e t e r m i n e d . % Unreacted n-butyllithium Mw

T M S butyl

MW

T M S PHE

„, y

(Area) (Area)

T M S

butyi

T M S phenyl

A m e r l c a n

+

(Area)

TMS

butyl

chemical

Society Library 1155 16th St. N. W.

In Polyamine-Chelated Alkali Metal Compounds; Langer, A.; Washington, 0. C.Washington, 20036 DC, 1974. Advances in Chemistry; American Chemical Society:

48


W h e n a l l of the gas h a d e v o l v e d , the h e a t w a s r e m o v e d , the s o l u t i o n w e i g h e d , a n d a s a m p l e a l l o w e d to react w i t h t r i m e t h y l s i l y l c h l o r i d e a n d analyzed by G L C . °7 Y i e l d — 0

(Area) T M S b u t y i (moles B u L i ) (130) (area)

benzene


[ ( I n i t i a l w t benzene present) — (moles B u L i ) 7 8 ] Recommended Preparation of P h e n y l l i t h i u m - T M E D A in Benzene. A 5-liter flask fitted w i t h a t h e r m o m e t e r , stirrer, reflux condenser, a n d p r e s s u r e - e q u a l i z i n g d r o p p i n g f u n n e l was flushed w i t h a r g o n a n d c h a r g e d w i t h 878 grams (13.65 m o l e s ) of n - b u t y l l i t h i u m ( 2 7 . 1 % ) i n b e n z e n e a n d 2,560 m l of benzene. ( I t is not necessary to use n - b u t y l l i t h i u m at this c o n c e n t r a t i o n because the 1:1 c o m p l e x is not s o l u b l e i n b e n z e n e b e y o n d a b o u t 1 9 % p h e n y l l i t h i u m at r o o m t e m p e r a t u r e . T h e extra b e n z e n e n e e d not be a d d e d w h e n a n in situ r e a c t i o n is p l a n n e d . ) T h e s l o w a d d i t i o n of 1,960-ml (13.0 m o l e s ) of T M E D A w a s b e g u n . T h e t e m p e r a t u r e w a s a l l o w e d to rise to 5 0 ° C w i t h a b o u t o n e - t h i r d of the T M E D A a d d e d . T h e gas e v o l u t i o n w a s v i g o r o u s at this p o i n t , a n d the rest of the T M E D A was a d d e d o v e r 1.5 hrs as b u t a n e e v o l u t i o n g r a d u a l l y s l o w e d . (Good c o o l i n g i n the condenser was necessary to p r e v e n t the c a r r y o v e r of b e n z e n e w i t h the b u t a n e . ) T h e s o l u t i o n was t h e n heated c a u t i o u s l y to 7 9 ° C t h e n c o o l e d q u i c k l y u n d e r a r g o n . Y i e l d w a s 1 0 0 % — 6 , 1 0 0 grams of an 18.89% p h e n y l l i t h i u m solution. P h e n y l l i t h i u m : T M E D A mole ratio w a s 1.04 b y G i l m a n d o u b l e t i t r a t i o n ( 1 7 ) . Thermal Stability of O r g a n o l i t h i u m - T M E D A Complexes. A b o u t 400 m l of the o r g a n o l i t h i u m - T M E D A c o m p l e x was p l a c e d i n a bottle a n d t h e n a n a l y z e d u s i n g the G i l m a n d o u b l e t i t r a t i o n (17). T h e bottle was p l a c e d i n a c i r c u l a t i n g constant-temperature o i l b a t h at the d e s i r e d t e m p e r a t u r e ( u s u a l l y 35° C ) a n d left for 30 days. T h e s o l u t i o n w a s reanalyzed. % D e c o m p o s i t i o n of a c t i v e m a t e r i a l / d a y _

( N e t contained)

initiai

( N e t contained)

— ( N e t contained)

fj

n a

i

initial

(30 days) Preparation of ( Benzyllithium >2--TMED A in Toluene. A 12-liter flask e q u i p p e d w i t h p r e s s u r e - e q u a l i z i n g d r o p p i n g f u n n e l , stirrer, reflux condenser, a n d t h e r m o m e t e r was p u r g e d w i t h a r g o n a n d c h a r g e d w i t h 7,096 grams o f 2 2 . 8 % n - b u t y l l i t h i u m i n toluene. T h e system w a s sealed f r o m the a i r b y a n o i l b u b b l e r u n d e r s l i g h t p o s i t i v e a r g o n pressure. A b o u t 3 0 % of 1,470 grams of T M E D A ( 1 % excess) was a d d e d over 40 m i n to b r i n g the r e a c t i o n to 56 ° C w i t h v i g o r o u s gas e v o l u t i o n . T h e c o m p l e t e a d d i t i o n took 95 m i n . T h e flask w a s h e a t e d to 70 ° C a n d t h e n c o o l e d to r o o m t e m p e r a t u r e . T h e clear, d e e p red-orange s o l u t i o n w e i g h e d 7,100 g r a m s ; i t was a n a l y z e d as 36.0 w t % b e n z y l l i t h i u m b y G i l m a n d o u b l e titration w i t h 1 0 1 % yield. Analysis b y G L C using trimethylsilyl chloride d e r i v a t i v e a n d m e s i t y l e n e as a n i n t e r n a l s t a n d a r d gave 3 5 . 5 % c o n c e n t r a t i o n a n d a y i e l d of 1 0 0 % .


2.

SMITH


Ring-isomer Content in B e n z y l l i t h i u m - T M E D A Complexes. O n l y solutions of b e n z y l l i t h i u m - T M E D A complexes w i t h little or n o b u t y l l i t h i u m w e r e a n a l y z e d . A 2 - m l a l i q u o t of the solution i n a s y r i n g e w a s injected i n t o a s m a l l bottle c o n t a i n i n g 10 m l of ether a n d 3 m l of d i m e t h y l sulfate u n d e r argon. T h e r e a c t i o n was vigorous. A f t e r 20 m i n the s o l u t i o n was washed w i t h water, dried over anhydrous N a S 0 , and analyzed b y G L C u s i n g a 10-ft, 1 0 % T r i t o n - S 3 0 5 / C h r o m a s o r b W at 9 0 ° C . ( O n l y p a r t i a l r e s o l u t i o n of m e t a a n d p a r a isomers w a s o b t a i n e d , a l t h o u g h i t c o u l d have b e e n o b s e r v e d w h e t h e r a r e l a t i v e l y s m a l l a m o u n t of p a r a isomer was present.) T h e percent of r i n g isomer w a s c a l c u l a t e d f r o m the t o t a l a m o u n t of r i n g i s o m e r p l u s the ethylbenzene present. Preparation of B e n z y l l i t h i u m - T E D Solid Complex. A 5 0 0 - m l flask e q u i p p e d w i t h a stirrer, t h e r m o m e t e r , a n d reflux condenser after p u r g i n g w i t h a r g o n was c h a r g e d w i t h 184 grams 1 5 . 2 % n - b u t y l l i t h i u m i n hexane, a n d 47.9 grams T E D ( 2 % d e f i c i e n c y ) was a d d e d . T h e s o l u t i o n w a s t h e n h e a t e d after a d d i n g 48.2 grams of toluene ( 1 2 % excess). T h e s o l u t i o n w a s refluxed 3.25 hrs. I t w a s t h e n c o o l e d to 10 ° C , s t i r r e d for 1 h r , a n d filtered u n d e r argon. T h e y e l l o w crystals w e r e d r i e d for 6 hrs (1 m m ) at r o o m t e m p e r a t u r e . T h e y i e l d was 8 9 % or 80.6 grams of s o l i d c o m p l e x . Preparation of A l l y l l i t h i u m - T M E D A Solid Complex. A 1-liter flask e q u i p p e d w i t h a gas inlet t u b e , stirrer, a n d t h e r m o m e t e r w a s p u r g e d w i t h n i t r o g e n a n d c h a r g e d w i t h 437 grams of 1 0 . 0 % s e c - b u t y l l i t h i u m i n hexane. T h e s o l u t i o n was c o o l e d to — 5 ° C , a n d 77.7 grams of T M E D A w e r e a d d e d w i t h c o o l i n g to m a i n t a i n — 5 ° C . A b o u t 43.0 grams ( 5 0 % excess) of p r o p e n e w e r e d i s s o l v e d i n the s o l u t i o n i n 30 m i n . T h e s o l u t i o n w a s t h e n a d d e d to a 1-liter h e a v y - w a l l pressure bottle, sealed, a n d h e a t e d to 4 5 ° C w i t h m e c h a n i c a l s h a k i n g ( a P a r r low-pressure r e a c t o r ) . T h e s o l u t i o n was t h e n c o o l e d to 10 ° C a n d filtered. T h e y e l l o w - o r a n g e p r e c i p i t a t e was r i n s e d w i t h pentane a n d b l o w n d r y w i t h argon. T h e y i e l d w a s 90 grams of the s o l i d c o m p l e x d e s i r e d o r 8 0 % . (Pressure is o p t i o n a l i n final warm-up. ) 2


49

4

Preparation of C r o t y l l i t h i u m - T M E D A . A 5 0 0 - m l flask e q u i p p e d w i t h a stirrer, t h e r m o m e t e r , condenser, a n d gas-inlet t u b e w a s p u r g e d w i t h a r g o n a n d c h a r g e d w i t h 191 grams of 1 2 . 2 % s e c - b u t y l l i t h i u m i n cyclohexane. T h e s o l u t i o n was c o o l e d to — 5 ° C , a n d 41.4 grams ( 2 % d e f i c i e n c y ) of T M E D A was a d d e d w h i l e c o o l i n g to m a i n t a i n — 5 ° C . T o this s o l u t i o n 30.6 grams ( 5 0 % excess) of 1-butene was a d d e d at 0 ° C i n 20 m i n . T h e s o l u t i o n was a l l o w e d to w a r m to 25 ° C o v e r 30 m i n , h e a t e d to 40 ° C q u i c k l y , a n d t h e n c o o l e d to r o o m temperature. T h e d a r k , r e d orange s o l u t i o n t i t r a t e d as 3 . 3 9 N base or 1.13M w i t h a v o l u m e of 297 m l , c o r r e s p o n d i n g to a y i e l d of 9 2 % . G L C analysis of the t r i m e t h y l s i l y l d e r i v a t i v e of this s o l u t i o n gave the c o m p o s i t i o n of the s o l u t i o n as 29.5 ± 1 % l - l i t h i o - 2 - b u t e n e ( t e r m i n a l ) a n d 70.5 ± 1 % 2-lithio-3-butene ( i n t e r n a l ) at 5 5 ° C . A n a l y s i s of the s o l u t i o n at 2 0 ° C gave 2 9 . 0 % t e r m i n a l . Preparation of Lithiated Ν,Ν,Ν',Ν'-Tetramethylethylenediamine. A 5 0 0 - m l flask e q u i p p e d as a b o v e was c h a r g e d w i t h 157 grams of 1 1 . 4 % s e c - b u t y l l i t h i u m i n cyclohexane. T h e solution was c o o l e d to 0 ° C a n d 32.5 grams of T M E D A was a d d e d w h i l e s t i r r i n g w i t h f u r t h e r c o o l i n g to I m a i n t a i n 0 ° C . T h e s o l u t i o n was h e a t e d to 4 9 ° C for 1 h r ( w h e n gas e v o l u t i o n c o m p l e t e l y s t o p p e d ) , t h e n c o o l e d to r o o m t e m p e r a t u r e . T h e d a r k , b r o w n - r e d s o l u t i o n was almost clear a n d w e i g h e d 175 grams. G L C


50

POL Y A M I N E - C H E L A T E D A L K A L I M E T A L COMPOUNDS


analysis of the t r i m e t h y l s i l y l d e r i v a t i v e s h o w e d n o s e c - b u t y l l i t h i u m r e m a i n i n g . A n a l y s i s of the s o l u t i o n b y G i l m a n d o u b l e t i t r a t i o n gave a net p r o d u c t c o n c e n t r a t i o n of 1 8 . 5 % w i t h the m o l e r a t i o of t o t a l b a s e to c a r b o n - b o u n d l i t h i u m of 2.06. T h e y i e l d b a s e d o n this t i t r a t i o n w a s 9 5 % . Preparation of Lithiated Trimethylamine. A f t e r p u r g i n g a 5 0 0 - m l h e a v y - w a l l bottle w i t h a r g o n , i t w a s c h a r g e d w i t h 175 grams (0.325 m o l e ) of 1 1 . 9 % s e c - b u t y l l i t h i u m i n cyclohexane. T h i s s o l u t i o n w a s c o o l e d u n d e r a r g o n to — 1 0 ° C , a n d 38.4 grams (0.65 m o l e ) of t r i m e t h y l a m i n e was d i s s o l v e d i n the s o l u t i o n w i t h c o o l i n g to m a i n t a i n — 1 0 ° C . The b o t t l e w a s sealed off, p l a c e d i n a P a r r l a b o r a t o r y pressure reactor, a n d h e a t e d to 60 ° C for 3 hrs w i t h s h a k i n g . T h e clear, d a r k , b r o w n - y e l l o w s o l u t i o n was c o o l e d to a m b i e n t t e m p e r a t u r e a n d a n a l y z e d . T h e s o l u t i o n w e i g h e d 190 grams, a n d c o n t a i n e d no s e c - b u t y l l i t h i u m b y G L C analysis of the t r i m e t h y l s i l y l c h l o r i d e d e r i v a t i v e . T o t a l base analysis of t h e filtered s o l u t i o n w a s 1 9 . 2 % i n d i c a t i n g a p r o d u c t concentration of at least 6 . 6 % for a 6 0 % y i e l d . Preparation of Other Lithiated Tertiary Amines and Diamines. T h e p r o c e d u r e f o l l o w e d for these c o m p o u n d s was the same as that u s e d for the l i t h i a t e d T M E D A d e s c r i b e d above. Synthetic Reactions of Organolithium-Tertiary Diamine Complexs. When (benzyllithium) -TMEDA, phenyllithium-TMEDA, crotyllithiumT M E D A a n d l i t h i a t e d T M E D A or t r i m e t h y l a m i n e solutions w e r e used, f r o m 0.4 to 0.5 m o l e of the o r g a n o l i t h i u m c o m p l e x i n the h y d r o c a r b o n solvent was a d d e d to a 5 0 0 - m l flask u n d e r a r g o n a n d c o o l e d to the a p p r o p r i a t e t e m p e r a t u r e . I n the cases of b e n z y l h t h i u m - T E D a n d a l l y l l i t h i u m T M E D A the s o l i d complexes w e r e a d d e d as a solvent. A m o l a r e q u i v a l e n t of the p a r t i c u l a r reactant was a d d e d via a p r e s s u r e - e q u a l i z i n g d r o p p i n g f u n n e l over a g i v e n i n t e r v a l w i t h s t i r r i n g at a constant t e m p e r a t u r e . ( A b o u t 1 0 % excess of the o r g a n o l i t h i u m c o m p o u n d w a s u s e d . ) A t a selected t i m e the s o l u t i o n was h y d r o l y z e d w i t h excess w a t e r . T h e o r g a n i c l a y e r was separated f r o m the aqueous l a y e r , w a s h e d t w o or three times w i t h 1 0 % aqueous a m m o n i u m c h l o r i d e , a n d d r i e d over a n h y d r o u s N a S 0 . T h e solvent w a s r e m o v e d b y d i s t i l l a t i o n at r e d u c e d pressures. T h e c r u d e p r o d u c t w a s p u r i f i e d b y r e c r y s t a l l i z a t i o n or d i s t i l l a t i o n . I n a l l cases the i n f r a r e d spectra w e r e c o m p a r e d w i t h k n o w n s or w e r e e x a m i n e d to ascertain t h e i r agreement w i t h the assigned structures. T h e p h y s i c a l constants w e r e also c o m p a r e d w i t h l i t e r a t u r e values w h e n possible. A n a l y s e s w e r e m a d e i n cases w h e r e d o u b t existed c o n c e r n i n g the structure because s t a r t i n g materials h a v i n g s i m i l a r structures m a y h a v e b e e n c o n t a m i n a n t s ; the results w e r e i n agreement. 2

2

4

P H E N Y L L I T H I U M - T M E D A I N B E N Z E N E . Benzophenone. A d d e d b e n z o p h e n o n e d i s s o l v e d i n b e n z e n e at 5 ° C over 1 h r ; let w a r m 1 h r ; h y d r o l y z e d , u s e d extra b e n z e n e d u r i n g w o r k - u p ; r e c r y s t a l l i z e d f r o m 1:1 methanol-ethanol; m p 161°C (lit. m p 162.5°C); 9 5 % , triphenylcarbinol (36). Cyclohexanone. A d d e d cyclohexanone d i s s o l v e d i n T H F at 0 ° C i n 1 h r ; let w a r m 1 h r ; h y d r o l y z e d ; r e c r y s t a l l i z e d f r o m h e p t a n e ; m p 6 0 ° C (lit. m p 61 ° C ) ; 5 9 % , 1 - p h e n y l c y c l o h e x a n o l (37). ( B E N Z Y L L I T H I U M ) 2 - T M E D A I N T O L U E N E . Trimethylsilyl chloride. A d d e d t r i m e t h y l s i l y l c h l o r i d e d i s s o l v e d i n ether at — 5 ° C over 1 h r ; let


2.


SMITH

51

w a r m 0.5 h r ; h y d r o l y z e d ; d i s t i l l e d p r o d u c t ; b p 5 9 ° - 6 2 ° C ( 5 m m ) 1 8 4 ° - 5 ° C ) ; 8 1 % , benzyltrimethylsilane

(lit. bp

(38).

1- Bromobutane. A d d i t i o n at — 2 0 ° C over 1 h r ; let w a r m 0.5 h r ; hydrolyzed; distilled product; bp 6 1 ° - 6 4 ° (0.5 m m ) (lit. b p 8 1 ° C ( 2 0 2 m m ) ) ; 8 4 % , n-amylbenzene (36). Benzonitrile. A d d e d b e n z o n i t r i l e at — 5 ° C over 1 h r ; let w a r m 1.5 hrs; u s e d 2 0 % H C 1 for h y d r o l y s i s ; r e c r y s t a l l i z e d f r o m e t h a n o l ; m p 5 3 ° 5 4 ° C ( l i t . m p 6 0 ° C ) ; 1 6 % c r u d e , b e n z y l p h e n y l ketone (36). Ethyl acetate. A d d e d 0.5-mole e q u i v a l e n t s e t h y l acetate at 0 ° C over 1 h r ; let w a r m 0.5 h r ; h y d r o l y z e d ; d i s t i l l e d ; b p 1 2 2 ° - 1 2 5 ° C ( 0 . 4 m m )


[ht. b p 1 2 2 ° C ( 0 . 4 m m ) ] ;

4 3 % , dibenzylethanol

(39).

Ethyl benzoate. A d d e d 0.5-mole e q u i v a l e n t s of e t h y l b e n z o a t e at 5 ° C over 1 h r ; let w a r m 0.5 h r ; h y d r o l y z e d , r e c r y s t a l l i z e d f r o m h e p t a n e ; mp

55°-79°C

(crude)

(lit.

mp

86°C);

22%,

l,2,3-triphenyl-2-propanol

(40). Cychpentanone. A d d e d c y c l o p e n t a n o n e at — 4 0 ° C o v e r 6 m i n ; let w a r m to 0 ° C ; h y d r o l y z e d ; d i s t i l l e d , r e c r y s t a l l i z e d f r o m h e p t a n e ; m p 55°C

(lit. m p

59°C);

35%,

1-benzylcyclopentanol

(37).

Cyclohexanone. A d d e d c y c l o h e x a n o n e at — 5 ° C over 1 h r ; let w a r m for 1 h r ; h y d r o l y z e d ; recrystallized from heptane; m p 5 5 ° C (lit. m p 61°C); 59%,

1-benzylcyclohexanol

2- Butanone.

(37).

A d d e d 2 - b u t a n o n e at — 1 5 ° C over 1 h r ; let w a r m for

0.5 h r ; h y d r o l y z e d ; d i s t i l l e d ; b p 9 2 ° - 9 4 ° C ( 0 . 5 m m )

[lit. b p

110°-112°C

( 4 m m ) ] ; 5 3 % , 2 - b e n z y l - 2 - b u t a n o l (41). Diisopropyl ketone. A d d e d d i i s o p r o p y l ketone at — 5 ° C o v e r 1 h r ; let w a r m 0.5 h r ; h y d r o l y z e d ; d i s t i l l e d ; b p 9 6 ° C ( 0 . 1 m m ) [ l i t . b p 9 9 ° C ( 1 m m ) ] ; 8 2 % , 3 - b e n z y l - 2 , 4 - d i m e t h y l - 3 - p e n t a n o l (42). Benzaldehyde. A d d e d b e n z a l d e h y d e at — 3 5 ° C over 2 0 m i n ; h y d r o l y z e d ; distilled; b p 6 2 ° C (0.5 m m ) [lit. b p 8 1 ° C ( 1 0 m m ) ] ; 8 0 % n-amylbenzene (36). Benzophenone. A d d e d b e n z o p h e n o n e d i s s o l v e d i n toluene at — 1 5 ° C over 18 m i n ; let w a r m o v e r 5 0 m i n ; h y d r o l y z e d ; r e c r y s t a l l i z e d f r o m ethanol; mp

86°C

(lit. m p

89°C);

92%,

1,1,2-triphenylethanol

(36).

B E N Z Y L L I T H I U M - T E D . 1-Bromobutane. A d d e d 1 - b r o m o b u t a n e to c o m p l e x d i s s o l v e d i n ether at reflux over 1 h r ; r e f l u x e d o v e r n i g h t ; h y d r o lyzed; distilled; bp 6 2 ° C (0.5 m m ) (lit. bp 8 1 ° C ) ; 8 0 % , n-amylbenzene (36). Bromobenzene. A d d e d m o l e e q u i v a l e n t s b r o m o b e n z e n e to c o m p l e x d i s s o l v e d i n d i e t h y l ether at reflux over 6 5 m i n ; s t a n d o v e r n i g h t ; h y d r o l y z e d ; r e c r y s t a l l i z e d f r o m m e t h a n o l ; m p 5 0 ° C ( l i t . m p 5 6 ° C ) ; 3 2 % , 2b e n z y l b i p h e n y l (44). lodobenzene. S a m e p r o c e d u r e as for b r o m o b e n z e n e ; m p 4 9 ° C ( l i t . mp 5 6 ° C ) ; 2 0 % , 2-benzylbiphenyl

(43).

Benzonitrile. A d d e d b e n z o n i t r i l e to c o m p l e x d i s s o l v e d i n T H F at — 1 0 ° C over 1 h r , s t i r r e d at — 1 0 ° C for 0.5 h r ; l e t w a r m for 1 h r ; h y d r o l y z e d n o r m a l l y , b u t a d d e d 2 0 % H C 1 to c r u d e s o l i d p r o d u c t i n i s o l a t i o n to c o m p l e t e h y d r o l y s i s of i m i n e ; r e c r y s t a l l i z a t i o n f r o m e t h a n o l ; m p 5 3 ° C ( h t . m p 6 0 ° C ) ; 5 9 % , b e n z y l p h e n y l ketone (36). Ethyl acetate. A d d e d 0.5-mole e q u i v a l e n t e t h y l acetate to the c o m p l e x d i s s o l v e d i n d i e t h y l ether at 3 5 ° C over 4 5 m i n ; let w a r m o v e r n i g h t ; h y d r o l y z e d ; o i l r e s i d u e isolated after r e m o v a l of v o l a t i l e s ; i n f r a r e d i n d i -



52

POL Y A M I N E - C H E L A T E D A L K A L I M E T A L COMPOUNDS

c a t e d that the t e r t i a r y a l c o h o l w a s present b u t i m p u r e ; 2 5 % c r u d e ; 1,1dibenzylethanol (39). Ethyl benzoate. A d d e d 0.5-mole e q u i v a l e n t e t h y l benzoate to c o m p l e x d i s s o l v e d i n T H F at 0 ° C over 0.5 h r ; let w a r m over 1.5 h r ; h y d r o l y z e d ; r e c r y s t a l l i z e d f r o m e t h a n o l ; m p 8 3 ° C ( l i t . m p 8 6 ° C ) ; 6 6 % , 1,2,3t r i p h e n y l - 2 - p r o p a n o l (39). Methyl vinyl ketone. A d d e d m e t h y l v i n y l ketone to c o m p l e x d i s s o l v e d i n T H F at — 1 0 ° C over 50 m i n ; let w a r m over 1 h r ; h y d r o l y z e d ; d i s t i l l e d ; p o t t e m p e r a t u r e m a i n t a i n e d b e l o w 7 5 ° C , yet a p p a r e n t d e c o m p o s i t i o n or r e a r r a n g e m e n t o c c u r r e d ; pot residue h a d a b p > 78 ° C (0.2 m m ) ; i n f r a r e d i n d i c a t e d c o n s i d e r a b l e h y d r o x y l a n d c a r b o n y l groups present i n p o t residue. Crotonaldehyde. A d d e d c r o t o n a l d e h y d e to c o m p l e x d i s s o l v e d i n d i e t h y l ether at 0 ° C over 20 m i n ; let w a r m over 1 h r ; h y d r o l y z e d ; n o p r o d u c t , o n l y p o l y m e r isolated. 2-Butanone. A d d e d 2-butanone to c o m p l e x d i s s o l v e d i n d i e t h y l ether at 0 ° C over 40 m i n ; let w a r m over 1 h r ; h y d r o l y z e d ; d i s t i l l e d ; b p 6 7 ° C (0.3 m m ) [ l i t . b p 1 1 0 ° - 1 1 2 ° C (14 m m ) ] ; 6 5 % , 2 - b e n z y l - 2 - b u t a n o l (41). Cyclopentanone. A d d e d c y c l o p e n t a n o n e to c o m p l e x d i s s o l v e d i n T H F at — 1 0 ° C over 1 h r ; let w a r m over 1 h r ; h y d r o l y z e d ; r e c r y s t a l l i z e d from heptane; m p 5 6 ° C (lit. m p 5 9 ° C ) ; 1-benzylcyclopentanol (37). Cyclohexanone. A d d e d cyclohexanone to c o m p l e x d i s s o l v e d i n d i e t h y l ether at —10 ° C over 1 h r ; let w a r m o v e r n i g h t ; h y d r o l y z e d ; r e crystallized from heptane; m p 5 5 ° C (lit. m p 6 1 ° C ) ; 4 5 % , 1-benzylc y c l o h e x a n o l (37). Diisopropyl ketone. A d d e d d i i s o p r o p y l ketone to c o m p l e x d i s s o l v e d i n d i e t h y l ether at — 1 0 ° C i n 5 m i n ; let w a r m to 1 0 ° C over 18 m i n ; h y d r o l y z e d ; d i s t i l l e d ; b p 1 1 0 ° C ( 1 m m ) [lit. b p 9 9 ° C ( 1 m m ) ] ; 6 0 % , 3 - b e n z y l - 2 , 4 - d i m e t h y l - 3 - p e n t a n o l (42). Benzaldehyde. A d d e d b e n z a l d e h y d e to c o m p l e x d i s s o l v e d i n T H F at 0 ° C over 1 h r ; let w a r m over 2 h r s ; h y d r o l y z e d ; r e c r y s t a l l i z e d f r o m ethanol; m p 6 5 ° C (lit. m p 6 7 ° C ) ; 8 1 % , 1,2-diphenylethanol (36). Benzophenone. A d d e d b e n z o p h e n o n e d i s s o l v e d i n d i e t h y l ether to c o m p l e x d i s s o l v e d i n d i e t h y l ether at — 1 0 ° C over 0.5 h r ; s t i r r e d 0.5 h r m o r e at — 1 0 ° C , t h e n let w a r m o v e r n i g h t ; h y d r o l y z e d ; r e c r y s t a l l i z e d f r o m m e t h a n o l ; m p 8 7 ° C ( l i t . m p 8 9 ° C ) ; 9 9 % , 1,1,2-triphenylethanol (36). Indanone. A d d e d i n d a n o n e d i s s o l v e d i n T H F to c o m p l e x d i s s o l v e d i n T H F at — 1 0 ° C for 45 m i n ; let w a r m over 1.5 h r s ; h y d r o l y z e d ; d i s t i l l e d a n d r e c r y s t a l l i z e d f r o m e t h a n o l ; m p 141 ° C ( l i t . m p 1 5 5 ° C ) ; 2 0 % , 1b e n z y l - l - i n d a n o l (44). Fluorenone. A d d e d fluorenone d i s s o l v e d i n d i e t h y l ether to c o m p l e x d i s s o l v e d i n d i e t h y l ether at 35 ° C over 25 m i n ; h y d r o l y z e d ; r e c r y s t a l l i z e d from cyclohexane; m p 1 3 3 ° - 1 3 6 ° C (lit. m p 1 4 3 ° C ) ; 8 3 % , 9-benzyl-9fluorenol (45). Lithium benzoate. A d d e d l i t h i u m benzoate to c o m p l e x d i s s o l v e d i n T H F at 35 ° C , h e a t e d to reflux for 25 m i n , c o o l e d , s t i r r e d 1 h r b e f o r e hydrolysis; hydrolyzed; recrystallized from ethanol; m p 56°C (lit m p 6 0 ° C ) ; 4 4 % , b e n z y l p h e n y l ketone (36). A L L Y L L I T H I U M - T M E D A . Benzophenone. A d d e d b e n z o p h e n o n e d i s s o l v e d i n d i e t h y l ether to s l u r r y of the c o m p l e x i n d i e t h y l ether at 20 ° C


2.


SMITH

53

over 0.5 h r ; s t i r r e d 1 h r ; h y d r o l y z e d ; d i s t i l l e d b p 1 2 8 ° C ( 0 . 6 m m ) bp

135°C

mm)];

(0.5

l,l-diphenyl-3-buten-l-ol

91%,

[lit.

(46).

Cyclohexanone. A d d e d c y c l o h e x a n o n e to s l u r r y of the c o m p l e x i n d i e t h y l ether at 2 0 ° C o v e r 2 0 m i n ; s t i r r e d 2 0 m i n ; h y d r o l y z e d ; d i s t i l l e d ; b p 6 4 ° - 6 8 ° C ( 8 m m [lit. b p 8 1 ° C ( 1 5 m m ) ] ; 5 2 % , 1-allylcyclohexanol(47).

C R O T Y L L I T H I U M - T M E D A I N H E X A N E . A d d e d acetone to c o m p l e x i n s o l u t i o n at — 2 0 ° C o v e r 0.5 h r ; let w a r m o v e r 4 0 m i n ; h y d r o l y z e d ; d i s tilled; bp

65°-71°C

(120

mm)

[lit.

bp

133°-135°C

(760

mm);

142°C.

(760 m m ) ] ; 1 1 % , 2,3-dimethyl-4-penten-2-ol a n d fmns-2-methyl-4-hexen2-ol; i n f r a r e d i n d i c a t e d no cis olefin b o n d s (48).


LITHIATED NJN^N^N'-TCTRAMETHYLETHYLENEDIAMINE (I)

IN H E X A N E .

T h e s e reactions w e r e a c i d i f i e d after h y d r o l y s i s a n d the o r g a n i c l a y e r d i s c a r d e d . T h e aqueous l a y e r w a s m a d e b a s i c w i t h N a O H s o l u t i o n a n d e x t r a c t e d w i t h ether. T h e ether l a y e r w a s d i s t i l l e d after d r y i n g o v e r anhydrous N a S 0 . 1- Bromobutane. A d d e d o n e - m o l e e q u i v a l e n t T M E D A to 1 2 % secb u t y l l i t h i u m i n hexane a n d h e a t e d at 5 5 ° C for 1 h r , c o o l e d to 0 ° C a n d a d d e d 0.95-mole e q u i v a l e n t of 1 - b r o m o b u t a n e over 0.5 h r ; l e t w a r m to 2

20°C;

4

hydrolyzed; distilled; bp

182°C

(760

mm)

[lit.

bp

183°C

(760

m m ) ] ; 4 9 % , N - n - p e n t y l - N ^ ^ N ' - t r i m e t h y l e t h y l - l ^ - e t h a n e d i a m i n e (49). A n a l y t i c a l l y calculates for C H 9 N : C , 6 9 . 7 5 ; H , 13.95; N , 16.29. F o u n d : 1 0

4

2

C , 6 9 . 7 5 ; H , 1 3 . 8 9 ; N , 16.49.

2- Bromobutane. A d d e d 1 - m o l e e q u i v a l e n t T M E D A to 1 1 . 4 % secb u t y l l i t h i u m i n hexane at 0 ° C , h e a t e d to 5 0 ° C f o r 1 h r a n d t h e n c o o l e d to 0 ° C ; a d d e d 1-mole e q u i v a l e n t 2 - b r o m o b u t a n e over 2 0 m i n ; let w a r m o v e r 0.5 h r ; w o r k e d u p ; h y d r o l y z e d ; d i s t i l l e d ; b p 5 2 ° C ( 2 . 9 m m ) ; 3 3 % , N- ( 2 - m e t h y l b u t y l ) - N ^ N ^ N ' - t r i m e t h y l - l ^ - e t h a n e d i a m i n e . Iodobenzene. A d d e d 1-mole e q u i v a l e n t T M E D A to 1 2 % s e c - b u t y l l i t h i u m i n hexane at 0 ° C , h e a t e d at 5 5 ° C for 1.5 h r s ; c o o l e d to 0 ° C a n d a d d e d 1 - m o l e e q u i v a l e n t i o d o b e n z e n e over 1 5 m i n ; s t i r r e d 1 h r at 2 0 ° C ; h y d r o l y z e d ; d i s t i l l e d , b p 6 9 ° C ( 0 . 3 m m ) [fit. b p 1 1 6 ° - 1 1 9 ° C ( 1 0 m m ) ] ; 30%, N - b e n z y l - ^ N ^ N ' - t r i m e t h y l - l ^ - e t h a n e d i a m i n e (49). Analytically c a l c u l a t e d for H,

C

1 2

H

2 0

No:

C , 7 5 . 0 0 ; H , 1 0 . 4 2 ; N , 14.58.

F o u n d : C , 75.01;

10.32; N , 14.41.

1-Bromooctane. A d d e d 1-mole e q u i v a l e n t T M E D A to 1 3 % secb u t y l l i t h i u m i n hexane at 0 ° C , h e a t e d at 5 0 ° C for 1.25 h r s , c o o l e d to 2 0 ° C ; a d d e d 1-mole e q u i v a l e n t 1 - b r o m o o c t a n e over 0.5 h r , s t i r r e d 0.5 h r m o r e ; h y d r o l y z e d ; d i s t i l l e d ; b p 8 5 ° C ( 0 . 5 m m ) [ht. b y 1 3 5 ° - 1 3 9 ° C ( 1 1 m m ) ] ; 4 0 % , N-n-nonyl-N,N',JV'-trimethyl-l,2-ethanediamine ( 5 0 ) . Bromocyclohexane. A d d e d 1-mole e q u i v a l e n t T M E D A to 1 5 . 5 % n - b u t y l l i t h i u m i n hexane at 0 ° C , h e a t e d to reflux 3.75 hrs a n d c o o l e d to 0 ° C ; a d d e d 1 - m o l e e q u i v a l e n t b r o m o c y c l o h e x a n e over 2 0 m i n at 0 ° C ; w a r m e d s l o w l y over 0.5 h r ; h y d r o l y z e d ; d i s t i l l e d ; b p 6 9 ° C ( 0 . 5 m m ) ; 1 8 % , N- ( c y c l o h e x y l m e t h y l ) - N j N ' j N ' - t r i m e t h y l - l ^ - e t h a n e d i a m i n e . Cyclopentanone. A d d e d 1 - m o l e e q u i v a l e n t T M E D A to 1 1 . 9 % secb u t y l l i t h i u m at 0 ° C , h e a t e d to 5 0 ° C for 1.25 hrs, c o o l e d to 0 ° C a n d a d d e d 1-mole e q u i v a l e n t c y c l o p e n t a n o n e o v e r 2 0 m i n ; s t i r r e d 2 0 m i n at 2 0 ° C ; h y d r o l y z e d ; d i s t i l l e d ; b p 8 1 ° C ( 1 . 5 m m ) ; 2 8 % , N-( 1 - h y d r o x y c y c l o p e n tylmethyl ) -IV^^N'-trimethyl-l^-ethanediamine.


54

POLYAMINE-CHELATED ALKALI M E T A L

COMPOUNDS

Valeraldehyde. A d d e d 1-mole e q u i v a l e n t T M E D A t o 1 5 . 5 % n - b u t y l l i t h i u m i n hexane a t 0 ° C , h e a t e d a t reflux 3.75 h r s , c o o l e d to —10 ° C , a n d a d d e d 1-mole e q u i v a l e n t v a l e r a l d e h y d e o v e r 20 m i n ; l e t w a r m over 0.5 h r ; h y d r o l y z e d ; d i s t i l l e d ; b p 8 4 ° C (0.7 m m ) ; 3 9 % , N-(2-hydroxylhexyl ) -N^^N'-trimethyl-l^-ethanediamine.


LITHIATED TRIMETHYLAMINE

( II ) IN H E X A N E .

L i t h i a t i o n of t r i m e t h

y l a m i n e was d o n e i n a pressure reactor d u r i n g the h e a t i n g step f o r a c t u a l lithiation of the tertiary amine. l-lodopropane. A d d e d 2 mole equivalents trimethylamine to 15.1% n - b u t y l l i t h i u m i n hexane a t 0 ° C ; s o l u t i o n h e a t e d a t 7 0 ° C f o r 5 hrs a n d c o o l e d t o — 1 0 ° C ; 0.85-mole e q u i v a l e n t 1 - i o d o p r o p a n e a d d e d over 20 m i n ; w a r m e d o v e r 0.5 h r ; h y d r o l y z e d ; d i s t i l l e d ; b p 9 2 ° C (760 m m ) [ l i t . b p 9 5 ° C (760 m m ) ] ; 3 2 % , N , N , N - n - b u t y l d i m e t h y l a m i n e ( 5 1 ) . 1-Bromooctane. A d d e d 2 - m o l e e q u i v a l e n t s t r i m e t h y l a m i n e t o 1 3 . 2 % s e c - b u t y l l i t h i u m i n hexane, h e a t e d to 60 ° C f o r 3 hrs, c o o l e d to —10 ° C , a n d a d d e d 1-mole e q u i v a l e n t 1 - b r o m o o c t a n e o v e r 20 m i n ; l e t w a r m t o 2 0 ° C ; h y d r o l y z e d ; d i s t i l l e d ; b p 5 2 ° C (2.9 m m ) [lit. b p 2 0 9 ° C (741 m m ) ] ; 3 3 % , Ν , Ν , Ν - d i m e t h y l n o n y l a m i n e (52). Benzaldehyde. A d d e d 2 m o l e equivalents t r i m e t h y l a m i n e to 1 1 . 9 % s e c - b u t y l l i t h i u m i n c y c l o h e x a n e a t —10 ° C , h e a t e d to 50 ° C f o r 6 hrs, c o o l e d to — 1 0 ° C ; a d d e d 0.85-mole e q u i v a l e n t b e n z a l d e h y d e o v e r 0.5 h r ; let w a r m over 0.5 h r ; h y d r o l y z e d ; d i s t i l l e d ; b p 7 2 ° C (0.25 m m ) [ l i t . b p 1 7 0 ° C (760 m m ) ] ; 4 9 % , ( l - h y d r o x y - l - p h e n y l e t h y l ) d i m e t h y l a m i n e (53). Acknowledgment I t h a n k E . D . K u e h n a n d Κ. B . L y n s k e y w h o assisted i n the l a b o r a tory work.

Literature Cited 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18.

Eberhardt, G. G., Butte, Jr., W. Α., J. Org. Chem. (1964) 29, 2928. Langer, Jr., A. W., Trans. Ν.Y. Acad. Sci. (1965) 27, 741. Screttas, C. G., Eastham, J. F., J. Amer. Chem. Soc. (1965) 87, 3276. Rausch, M. D., Ciappenelli, D. J., J. Organometal. Chem. (1967) 10, 127. Langer, Jr., A. W., U.S. Patent 3,536,679 (1970). Crawford, R. J., Erman, W. F., Broaddus, C. D., J. Amer. Chem. Soc. (1972) 94, 4298. Agami, C., Bull. Soc. Chem. Fr. (1971) 1619. Mallan, J. M., Bebb, R. L., Chem. Rev. (1969) 69, 693. Langer, Jr., A. W., Polym. Prepr., Am. Chem. Soc., ACS Div. Polym. Chem. (1966) 137. Eberhardt, G. G., Davis, W. R., J. Polym. Sci., Part A (1965) 3, 3753. Stucky, G. D., Amer. Chem. Soc., Div. Polym. Chem., Preprint, 13 (2), 644 (New York, Aug. 1972). Eberhardt, G. B., Butte, Jr., W. Α., U.S. Patent 3,321,479 (1967). Gilman, H., Pacevitz, Η. Α., Baine, O., J. Amer. Chem. Soc. (1940) 62, 1514. Gilman, H., Schwebke, G. L., J. Org. Chem. (1962) 27, 4259. Seyferth, D., Weiner, Μ. Α., J. Org. Chem. (1959) 24, 4797. Chalk, A. J., Hoogeboom, Τ. J., J. Organometal. Chem. (1968) 11, 615. ASTM Standard Method No. E-233 (n-Butyllithium Analysis). Broaddus, C. D., J. Org. Chem. (1970) 35, 10.


2. SMITH Tertiary Diamine Organolithium Complexes


19. 20. 21. 22. 23. 24. 25. 26. 27.

55

West, R., Jones, P. C.J. Amer. Chem. Soc. (1968) 90, 2656. Gau, G., Bull. Soc. Chim. Fr. (1972) 1942. Buhler, J. D., J. Org. Chem. (1973) 38, 904. Magruder, W. J., Dissert. Abstr. (1966) 27, 759B. Eisch, J. J., Jacobs, A. M., J. Org. Chem. (1963) 28, 2145. Seyferth, D., Weiner, W. Α., J. Org. Chem. (1959) 26, 4797. Lampher, E. J., J. Amer. Chem. Soc. (1957) 79, 5578. Seyferth, D., Juta, T. J., J. Organometal Chem. (1967) 8, P13. Johnson, C. S., Weiner, Μ. Α., Waugh, J. S., Seyferth, D., J. Amer. Chem. Soc. (1961) 83, 1306. 28. Langer, Jr., A. W., U.S. Patent 3,541,149 (1970). 29. Lepley, A. R., et al.,J.Org. Chem. (1966) 31, 2047. 30. Ibid, 2051. 31. Ibid, 2055. 32. Ibid,-2061. 33. Ibid, 2064. 34. Smith, W. N., unpublished data. 35. Peterson, D. L., J. Amer. Chem. Soc. (1971) 93, 4027. 36. "Handbook of Chemistry and Physics," 53rd ed., The Chemical Rubber Co., Cleveland, O. 1972. 37. Stach, D., Winter, W., Arzneimettel-Forsch. (1962) 12, 194; Chem. Abstr. (1962), 57, 16453. 38. Brook, A. G., et al., J. Amer. Chem. Soc. (1960) 82, 5102. 39. Gamboa, J. M., Ossorio, R. P., Rapun, R., An. Real Soc. Espan. Fis. Quim. (1961) 57B, 607C; Chem. Abstr. (1962), 57, 700. 40. Rampart, P., Amagat, P., Ann. Chim. (1927) 8, 263. 41. Warnick, P., Saunders, Jr., W. H., J. Amer. Chem. Soc. (1962) 84, 4095. 42. Frank, C. E., Foster, W. E., Ind. Eng. Chem. (1954) 46, 1019. 43. Chel'tsova, Μ. Α., et al., Izv. Akad.HaukSSSR, Ser. Khim. (1965) 1, 124; Chem. Abstr. (1965) 62, 11707. 44. Nizamuddin, S., Ghosal, M., Chudhury, D. N., J. Indian Chem. Soc. (1965) 43, 569. 45. Cadogan, J. I. C., Hey, D. H., Sandersen, W. Α., P. Chem. Soc. (1960) 3203. 46. Vozza, J. F., J. Org. Chem. (1959) 24, 720. 47. Huet, J., Bull. Soc. Chim. Fr. (1964) 2677. 48. Kochi, J., J. Org. Chem. (1963) 28, 1969. 49. Grail, G. F., et al.,J.Amer. Chem. Soc. (1952) 74, 1313. 50. Shepherd, R. Α., Wilkinson, R. G., J. Med. Pharm. Chem. (1962) 5, 823. 51. Braun, H. C., Berneis, H. L., J. Amer. Chem. Soc. (1953) 75, 10. 52. King, H., Work, T. S., J. Chem. Soc. (1942) 401. 53. Klosa, J:. J. Prakt, Chem. (1963) 21, 1. RECEIVED March 12, 1973.


Polyamine-Chelated Alkali Metal Compounds

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