Heterocycles from heterocycles. 1,3-Diaryl-4,5-imidazolidinediones from 1,3,5-triarylhexahydro-1,3,5-triazines and oxalyl chloride

oo4o-4020193s6oo+oo 1993 Perganon

Press Ltd

Heterocycles from Heterocycles. 1,3-Diaryi4,5-irmdazolidinediones from 1,3,5-Tnarylhexahydro-1,3,54nazmes and Oxalyl Chlonde

Angelo G. Giumanir& * Faust0 Gorass~~,

Giancarlo Verardo,

Manlena Tolazv

and

Pa010 Strazzohni

Department

of

Chemical

Udine.

Via

Sc~cncer

de1

and

Cotontficio

Unlverslty

Technologies,

108,

33100

Udine.

of

Italy

(Recewed m UK 26 Juiy 1993, accepted 10 September 1993)

Abstract:

1.3-Dlaryl-4,5-imidazclidinedicnes

synthesized

from chloride

CXClYl

290

ethyl

acetate/dlchloromethane

55

261

ethyl

acetate

60

182

ethyl

acetate/trlchloromethane

90

251b

ethyl

acetate/dlchloromethane

G! (4-F-C,H,)

80

266

ethyle

li (3-Cl-C,H,)

93

247

ethyl

acetate/dlchloromethane

90

267

ethyl

acetate/dlchloromethane

67

268

ethyl

acetate/dlchloromethane

A!? (3-He-C,H,) Ic

(4-He-C,H,)

(4-?&H,) If (L-F-CsH,)

(3-F%,H,) acetate/dlchlorcmethane

(4&H,) llz (3-Br-CGH4) ‘Yield

of

recrystallized

product

bDecomposltlon

temperature.

and (4)

Hctcrocycles from hetemcycles

The parent

molecule itself,

dasohdine-2,3-lone),

an isomer of the well known compound

is not known and only

-4.5~inudazokdinedlone7

and

10611

two 1,3-denvataves,

hydantoln

namely

1,3-drbenzoyl-4,5_irdasolidinedione,8

(irm-

1,3-dimethyl-

were

described

to

date. Our synthetic

procedure

amount of 1 in dlethyl the

reaction

outcome. from

with

If the 1)

facilitating

decomposition

latter

analysis

solution. out

conceivable ethanol

in fast

the

ruled

eqmhbnum

termnation

to rationahze

with the tnmer pathway

zwittenonic

out the presence

(i3) were detected,

This

the

observation

reaction

of the

or ongmating

A should

species

with the naked

intermediate closure

be at work

1 may be active,

thus

chlonde

Q

generated.

This, in turn,

ethanolysis

to the constantly

Indirect

support

for

either this

undergoes

stabilization

e (le)

of 2 sparked

role

_6: but, besrde

lJ,

to react

of of 3

ring

closure

and

the

key

in

it is fast

of CH,Cl,,

with 5 to

unable

to 6a_k or further

form

to undergo

intermediate

was offered

by the reaction

j.J 19

competitive

between

5 in its devious

1,3,5-

behaviour:

B, which did not lead to Se, but to N-ethoxy-

(15), detected

by direct inlet MS analysis

rmxture, together

side product,

tentatively

with another

alcohol

In fact,

oxalamrdes 14a_k.

and oxalyl chlonde

route

promptly

oxaiyl-di(4-anlsylarno)methane

-hydroxymethyl-di(4-anlsylamino)methane

the

the absence

which, apparently

rs added

by-product

hypothesis

-tn(4-anlsyl)hexahydro-1,3,5-tnazin

essential

(1)

of the

to l0, in turn bound to undergo

hand, expected ethanol

observed

from ethanolysrs

role to give

until

an

evolve

ion to produce

and furthermore survives

to

but both diethoxymethane

coming

the rnitzal intervention

would rapidly

to play an essential

to lJ,

out

of CH,Cl,,

the former

pointed

and ruled

that 2, d formed,

was found

enhanced

by a necessary

may be envisaged

of 1 is to be involved,

The monomer 2 is, on the other nng

of 5 to an equlmolecular

pathway B.

in

reaction

courses

hand, the drmenc

ethoxymethylchlonde

carrying

addition

immediately followed

Two different

On the other

Headspace and

ether at OV,

ethanol.

monomer (2), either

the induced

(Scheme

calls for the portionwise

identified

on the reaction

as N-chloromethyl-N’-

(l6)

I

I

(~-AII-N=CH~)~ 0

le

N-MI

I

p-in

+

p-An/NvN\p-An

I p-in

I!?

15

It IS possible attack of 3

that for ahphatic

1 to react,

decomposition

must be induced

by direct

G Wmumoetal

10612

Scheme 1

Ar Route A

Ar

I N

b b

f‘l

1 8 +

Ar-N&Ii2

f

2

Ar HNvNIAr la-k

\

+5

Ar ON%

/-

2

3 +5

0

0 N-Ar

Ar -N 73 ArMN

\

c1 cH,Cl

14 + IztOH -EtOCH,CI 0

/

0

+EtOH

*

-EtOCH,Cl Ar NNACH

cH~cl I 2 Cl

-CH,Ci, Cc1,Cl

6a-k

lo Ar

Ar xNAN'--CH

2

x

PC + 0

ci

0 0

0

Cl 4

Cl +f

f

2

9

-Cl

Route s

B

Heterocycles from hctcxocycles

No systematrc between the

work

&g and _5, but

condltrons

substrates.

for

a

the

few useful

reactin

Good solvents

obtarned

was carrzed

results

were

ethanol gave better

nomethane

route

which

when 1 was added

observatrons were

to

5. The

of

the reactins

were made m adlustrnq

essentilly use

6 in

apphed

to

were detrrmental;

the

of

anhydrous

solvents

to 6 was attempted a variety

by

reactin

of

amrnal N,N’-drphenylamr-

of expenmental

was by far the matn product,

conditrons,

accompanred

Schsme

but m all instances

2

,CH,

m.

Ar

= Ph

m:

Ar

= 4-N02-C6H4

+EtOH -a 0

and

by much lower yrelds of &

(Scheme 2).

(ArW

other

the best

yields

(17a) with 2 under

the oxamrde &

expenmental la,

yield

for 1, hke droxane and chloroform,

absolute

An alternate

of

out to optrnuxe the

10613

/

0

0

7-f ArRNvN-Ar

0

Ar-N

0

Y-3 N-Ar

‘H

H’

&&

(yie.

80-90X;)

141

(yic.

quantitative)

&

(yie.

a

(traces)

8-16x)

10614

G VERARDO et al

In the above of acltity

scheme the cause for the low yields is to be found

which tres up the mtermetite

that practically

@)

all of & was formed m this reactin

All the products

6a_k showed msolubllity

u

high melting pcunts which are also lndlcatlve The

steadfastness

Interactins.

ln an unreactive

of

the crystal

m fact, the isolated

before

m the productin

form. In fact,

alcohol ad&tin.

most common solvents

of thw

structure

extraordinary

points

molecules present

we found

and excepbnally

thermal stablhty

to strong

intermolecular

two tides of opposite

polar

polanties

Ar

In

view of

undertook

the

an X-ray

novelty crystal

of the

molecules

structure

Worth notrcrng are the following

and these

deternunatin features

propeties

of

the

sohds,

we

of &.

of & (Figure

1, mean values are quoted)

0

0

H 126

117

107

Ph

,-c_"+::zyph

23

20

Figure

The shght

Average

1.

twisting

values

molecular

m the same dvectron

the same plane with respect as indicated

of

and definitively

(141

comparison show

leaving

a larger

elongated

(ca

repulsions

(Figure

angle

154

of about

A), the result 2)

A), above

carbon

groups,

angles

90°

(1 39 A) found

some conlugatin for a perfectly

armdes of this type

for the bonds

the

of the hkely

for a pure

with the hydrogens

has to take into account

around

&.

placzng them almost on

would not lnhlblt that

of

EI smaller than that expected

s contnbutlon

with open ch;lm oxarmdes 11.12

a torsional

ring,

bond

larger than for less conventinal

(1 36 A) 10 The angle at the saturated

sp3 hybnduatin,

and

of the phenyl

to the heterocychc

by the Ar-N distance

planar arylarmne,g

dimensions

that these

A

systems

OC-CO anus which 15 extraordmanly

charged

oxygen,

carbon

and nitrogen

Hetemcycles from heterocycles

The only

possible

value of 126’ agatnst distance 107’

response

is the

widening

of the OCC bond

observed

the nng

NCC bond angles are squeezed

6’N

OS9

6’ N

06’

II

Figure 2.

where

enclosed

hkely charges

allow

for

Conformations

oxanudes,

energy

O-O

to a meager value

of

of

Different

geometnes

configuration

III open

oxamides

hke 6+ can only exist in the high energy

are the closest.

perpendicular

electrostatic

to a

in the open chsun cases.

x

Planar nng

angles

117O for the open charn case which would cause a quite short

As a consequence

from 117’

of &

10615

III I

stenc

more

Entropic

or

requirements less

UI open oxanndes may

approaching

factors

play

form II,

a role

the

ideal

lowest

in the equilibrium

positions. Literature some

were

structural

collected by

comparison

with all other

of

which

the are

titance,

cd.

repulsion

(Figure

nature

any

special

conclusion.

medium

intensity

the obtained with

chloro-derivatives in scheme

found

is

the

19 @

in

the

products

Mass spectra

exception refers

0.04 A larger

of

the

mvanant

analysis

parent

observed

of the ion decompositions

to the ion derived

by high resolution

from @;

mass spectrometry

with the

here

by elemental

intensity

C=O

point to an imperfect

of 6a_k exhibited low

The than

differences

practrcally

a contradiction

6 was confirmed

6-J. The common features

105 was secured

as well as in &.

mvestigated,lz The

widened

ions for

of the

are shown

the composition whch

and

ruled

of the out the

of PhCOe

The consistently azindone

are few and

the N-atom seems to be more conlugated

properties.

3, which specifically

ion at m/z presence

&i and

m &

Noteworthy

and ca.

* 6 though,

with that of formaldehyde,

Oddly enough,

MS and spectroscopic

systems

than in formamide

1,3-rnndazohdme-4.5dlones

coincident

of

2)

3 and Table-a)

But, as we shall see, the 1 H NMR data will introduce The

their

bond

present

(Table

to a value of 126“ in all these

small to evince

actually

system

denvatives

s~~1a.r cases 13 Surnlarly the CC0 angle is strongly

1,2,3-tnsubstituted too

NC0 amide conlugation. ring.

the heterocycbc

substituted

of &a is some 0 02 A larger

N-CO bond that

more

0 04 A of the C,-C,

contraction

by the oxygen

data for

for

peak the

formally

ascribed

to

the

base peak in all spectra

N-methylenearylamine

of 6a_k. Of interest

(133 mu) from the parent ion of Q to produce

of an aryhsocyanate

molecule

(Table 3)

radical

cation

was

is the formal loss of an

what is likely the molecular ion

\

0

E)n

Me .-N

x

W

10

N

”

0

Ph

N’tle

0

NNMe S

c

IPh’N”NNPh

Ph-

Me

0

9-t

0

‘Average

(i-Pr)jlN

0

values

z

between

N(i-Pr),

Y-4

0

Y-tNW) (Me) ,N

!?!I

6a’

and

175

143

’ 3!3

1.4(i

x

11

1.35

1.38

1.38

(A)

bReported

1.46

145

145

1-44

1.41

(A)

.

1.52

to

102.8

106.2

103

0

.N

C

(“)

N.

refer

1 52

1.49

(A)

values

122

1.19

L.21

(A)

N-C N-exoC N-CO C=O CC-CO

6

C

117.0

118

106

105

(“)

0

0

8

N. .C

S=C-N(Ph)-CO-CO

113.2

112

111

6

cc

N

(“)

C.

5

system

124

127

127

co)

118

127

126

(“)

3

0

0

0

0

(“)

work=

13b

13b

13ab

this

Ref

Hctc~les

10617

fromheterocycles

6a, m/z 252 0

P

m/z

133

NxPh

\ - Ph-N&l, *

-01.

Ph-N=Cm/z

119

m/z 224

-NC0

I

- Ph-N=C=O

Ph-N-

/

v?

-CH21e

m/z

77

-Cd+,

* we m/z

51

m/z 105

9

Ph-N=CH m/z

104

Comparison of this spectral pattern with the fragmentataon of the closely related open oxarmde N,N’-dimethyl-N,N’-lphenyloxarmde

(19) indicated that the trigger

for all

of the observed fragments is the cleavage of the sigma bond between the two carbonyls (Scheme 4)

2.43(s, 6H), 5.46(s, 2H), 7.107.63(88, a)

2.36(s, 6H), 5.40(s, 2H), 7.27 (d, 4H Jx9.00). 7.65(d, 4H, Jl9.00) 1.33(s, 18H). 5.44(s, ZH), 7.48 (d, 4H, Jn9.00). 7.68(d, 4H, J=9.00)

7.70-7.80(m,

5.48(s, 2H). 7.19-7.45(m, 6H), 2H)

5.49(s, 2H), 6.99-7.12(m, 2H), 7.40-7.55(m, 4X), 7.66-7,75(m, 2H) 5.47(s, 2H), 7.15-7.30(m, 4H), 7.70-7.85(m, 4H)

1715~8, 14858, 1400~8, 1290s. 118Om, 79010, 685111

1735~8, 16108, 151Os, 14OOs, 13008, 128Os, 815s

2930m, 1725vs, 15lOm, 1430m, 13858, 1300m, 1270m. 830s

1740~8, 1500vs, 14606, 1410~9, 13108, 12708, 1230s. 8108, 755~s

1730~8, 16108, 15908, 149ove, 14608, 14208, 14008, 11908, 770s

173OV8, 171OV8, 15006, 14009, 1240~11,116Om, 1090m. 830s

!&

Sr

5.66(s, 2H), 7.27-7.35(1n, 2H). 7.47-7.57(m, 4H), 7.93(d, 4H, Js8.00)

1725~8, 159Os, 1490vs, 14556, 1405V8, 12908, 1275s, 745~s. 680s

6a

1H NMRb (b , ppm; J, Hz)

IRa (cm-l)

Propertles of 1,3-Dlaryl-4,5-imldazolidinediones (5)

Compound

Table 3 rel%)

(continued)

288(M+, 26), 137(g), 123 (loo), 122(47), 95(29), 75 (9), 57(3)

288(M+, 31), 137(6), 123 (loo), 122(45), 96(5), 95 (29), 75(10)

288(M', 59), 137(11), 124 (17), 123(100), 122(85), 109(7), 95(38), 75(18), 57(5)

364(M+, 32). 349(42), 175 (9), 167(20), 161(47), 160 (80), 146(100), 132(18), 118(19), 106(6), 91(7), 77 (7), 44(21)

280(M+, 60), 133(21), 120 (22), 119(100), 104(7), 91 (70)) 77(8), 65(23), 51(8)

280(M+, 69). 133(13), 120 (22), 119(100), 118(57), 104 (6), 91(60), 77(8), 65(21), 53(6)

252(M+, 23), 119(6), 106(7), 105(100), 77(38), 64(4), 51 (16)

MSC (m/z,

5.48(s, 2H), 7.47(d, 4H. J=9.00) 7.72-7.80(d, 4H. J=9.00)

5.50(s, 2H), 7.32-7.47(m, 4H), 9), 410(M+, 21), 408 7.75-7.93(m, 4H)(H+, lo), 199(5), 1::;:::' 185(99), 183(100),157(19), W;l9), 90(13), 77(26), 51

1735vs, 14958, 1395vs, 1270m, 1090m, 825vs, 810111

1725vs, 15808, 1470~8, 1415s, 14oovs, 13056, 12608, 1090s, 760vs, 665s

6k

aSpectra were recorded in KBr. CSpectra recorded in CDC13 eolution using TM Upectra recorded via direct inlet.

as Internal standard.

324(H+, 3), 322(M+, 17), 320 27). 155(5) 153(15) :!;i42), 139(1OOj 138(45j, 111(27), 77(6), 7&15)

324(M+, l), 322(M+, 8), 320 14), 155(l) 153(5) %32), 139(1OOj 138(31j 111(21), 77(7), 75(12), Si (7)

5i

5.49(s, 2H), 7.25-7.48(m, 4H), 7.70-7.81(m, 4H)

1725~8, 1590s. 14708, 141Os, 1270m, 1105m. 870m, 775s. 670m

MSc (m/z, rel%)

si

IH NMRb (6 t ppm; J, Hz)

IRa (cm-l)

Compound

Table 3. (continuation)

ft

P

Heterocycles from heterocycles

Table 4.

Most Significant

Gecmetrlcal

Characteristics

of

10621

the

Refined

Molecules

Bond Lengths (A) O(1) - C(1) O(2) - C(2) O(3) O(4) N(1) N(1) N(1) N(2) N(2)

-

N(2) - C(10) N(3) - C(16) N(3) - C(18) N(3) - C(19) N(4) - C(25) N(4) - C(18) N(4) - C(17) C(16) - C(17) C(1) - C(2)

1.203(7) 1.216(7) 1 222(7) 1 205(8) 1.377(8) 1 422(8) l-458(7) 1.379(8) 1.467(8)

C(16) C(17) C(1) C(4) C(3) C(2) C(3)

Bond Angles C(4) - N(1) - C(3) C(1) - N(1) - C(3) C(1) - N(1) - C(4) C(3) - N(2) - C(10) C(2) - N(2) - C(10) C(2) - N(2) - C(3) C(18) - N(3) - C(19) C(l6) - N(3) - C(19) C(16) - N(3) - C(18) C(18) - N(4) - C(17) C(25) - N(4) - C(17) C(25) - N(4) - C(18) O(3) - C(16) - N(3) N(3) - C(18) - C(17) O(3) - C(16) - C(17) N(4) - C(25) - C(30) N(4) - C(26) - C(26) O(1) - C(l)-- N(i) N(1) - C(1) - C(2) O(l) - C(1) - C(2) N(2) - C(2) - C(1)

The contactig the

molecules

the

are

each other

pars-posrtron

alternatig to

119.8(S) 111 7(S) 128.6(S) 120.8(S) 127.1(S) 112.1(S) 121.1(S) 127.3(S) 111.6(S) 112.9(S) 126.8(S) 120.3(S) 127.5(S) 107.3(S) 125.2(6) 119.9(6) 120.4(6) 126.5(6) 107 4(S) 126.2(6) 106.2(S)

by a shght &ia/ and

phenyl

sectxnns

are

oxygens

and the electron

mdrcatrve

1 H NMR spectra the

methylene

between aruhne,l7 denvatlvea

the

cryatala

of the where

the

lmpovenshed

the

other.

like

heterocychc The

8.00

3). Whereas 5 showed ppm

data

(Table and

the

sryl

two types 3),

the

of a phenyl made

posrtrons between

of

the

21.0(9) -24.0(9) 19.3(8) -22.0(8)

columns, nng

and

up of piles

of one 19 almoat theae

negatively

of

parallel molecular charged

nng. pattern

5.40 and

protona

appeared

of resonances:

posrtions

singlet

for

I.II three

well separated

all of them were located

definitively

of a somewhat

with a sharp

5.66 ppm from the standard

N-methyl-N-formylanAnel e

are an mdlcatron

columns; are

nng

relative

the expected

at 6 values

column,

interactin

phenyl

parallel

of the me ta-Poe&on adjacent

between

N,N_drmethylanrhne18 These

of

126.3(6) 127 S(5) 102 7(4) 105.2(S) 126.2(8) 128.6(6) 121.3(6) 117.9(5) 102.6(4) 119.1(S) 121.1(S) 120.1(6) 122.2(6)

C(2) - C(1) C(2) - N(2) C(l8) - N(4) C(17) - C(16) C(17) - C(16) C(17) - N(4) C(4) - C(9) C(4) - C(5) C(3) - N(2) C(19) - C(24) C(19) - C(20) C(10) - C(15) C(10) - C(11)

C(1) - N(1) - C(4) - C(5) C(3) - N(2) - C(10) - C(15) C(l8) - N(3) - C(19) - C(24) C(l8) - N(4) - C(25) - C(30)

locahzed

(Table and

K,

-

Selected Torsion Angles (")

of some electrostatrc

para-substituted 7.10

nng

O(2) O(2) N(3) N(4) O(4) O(4) N(l) N(1) N(l) N(3) N(3) N(2) N(2)

overlapping nng

(“)

of 6 III CDCl, showed

group

tetramethylsllane regrons,

m

of a phenyl

molecules second

stacked

1 396(g) 1.375(8) 1 458(7) 1 409(8) 1 424(8) 1 452(7) 1 380(8) 1.502(9) 1.485(8)

strong

at

lower

and the electron

field

than

at for

correapondlng depletxon

away

G VERARLW et al

or __

Heterocycles from hetemycles

from the aromatic nng An lndrrect the

packing

into the amrde fun&on.

confrrmatron of the poslbve

of the molecules

&’

on top of the carbons

of phenyl

molecule

different

with shghtly

intermolecular

10623

attractron

polandion

ring,

with the oxygens

two such Interaction

posltiolllngs

playmg

This appears

an important

came from

of thr aromatic rugs

and +&’ m the crystals

bag

active

of one lust

for every

single

to be due to the strong

part m holtig

the molecules

polar

together

111

the crystals. A full view of the crystal side

columnar

with the

packrng rs offered

paclung

of the stacked

phenyls,

15 evidenced.

free

molecules,

by figure

The closest

one

molecule -6a’ and the related heterocyclic nng 3 6 A, well beyond any charge transfer Interactin.

distance

The huge and

the

cmncrdental

hypsochrormc

range values

-drphenyloxamzde carbonyl

for

cm- 1 for

and,

therefore

atom, and nng

strm

20

Thrs

be

simply

overwhelming

field

less effectrve

u-electron

6b_k

N-methylacetamrde

Clg) (1650-1665,

character may

shift of the carbonyl

1715-1740

electron

a

doublet) lesser

descreenlng

wlthdrawlng

transfer

packing

stretching

(Table

(20)

between

of the other

Figure 4a. General view of crystal

&

4a and 4b, where a side by

with any two columns barely

(1656

effect o-effect.

from the nrtrogen

by

frequency and

to the nng.

the

of

pratrcally

N,N’-lmethyl-N,N’effect

nitrogen

Thrs effect

of

to be

(1725 cm-l)

with

of electrons the

nng

was found

of &.

rs due to the combined delocalizatin

the phenyl

(6a”)

3) compared cm-l)

“touchmg”

overlaps

of enhanced

from the nrtrogen lone

pans

or

an

with some much

10624

G VMARDO~~ al

. ,

.

9

b

Heterocycles from heterocycles

10625

EXPERIMENTAL SECTION Oxalyl chlonde

llaterials.

available

(Aldrich,

prepare

the

method.1’

procedure.1

TLC plates

lhgh

Milhpore

(lengh uses

b Dry solvents

pressure

instrument,

30 cm, 1.d

Water-acetonitrile

liquid

(17)

obtained

equipped

with

following

mixtures were found

to

amine

the

according

standard

to a

procedures.2

*

from Merk, Italy.

analyses

an inverse

wavelength

use and used to

prepared

were obtied

pumps and a processing

before

accord.ing

were

chromatography

3.9 mm) and a &ted

two independent

of cd.

were

amines (2) were commercially

purified (1)

Diarylarmnomethanes

(neutral alumina on alumuuum plates)

Equ ~pment.

Waters

aromatic

they were conveniently

1,3,5-triarylhexahydro-1,3,5-tnananes

paraformaldehyde described

(3) and pnmary

Milano, Italy).

phase

were performed

with a

C,,

column

Bondapak

(240 nm) uv detector.

unit enabling

The system

eluent composition

su&able for our analysea

operating

control.

at a flow rate

1 ml/min.

Infrared

spectra

were recorded

with a Jasco

Mod. DS-702G spectrophotometer

by

the KBr pellet technique Electron automatic

impact

(70 eV) mass spectra

continuous

data

sample rnto the ion source, any

side

product

injecting

the

and

eluate ill

secured

as

for all isolated

internal

in recording

diffraction

that

was

2h

of

setting

width

and refined atoms

kept

in

The most intense

a Bruker The

Mod.

high

were

inert

with continuous

the

whole

to detect

performed

by

atmosphere

into

ms mo&onng

of

a the

peaks with therr relative

AC-F

insolubility

with a Carlo Frba

200 spectrometer of

6a_k

using

presented

a

Mod. 1106 elemental analyzer

fmm a crystal

single

25 reflections

crystal

of @

cd.

0.2 x 0.2 x 0.5

drffractometer

with 9 in range

with

graphite

10 s s s 16’

used for

5 26O (-8 J; h s 8, 0 5 k s 32, 0 s 1 5 14). o - 29

showed

no

intensities

slgruficant

The structure

of three

variation was solved

with SEELX 76.2 3 At convergence

were

analyses

of

~II order

(Table 5).

3 5 s

1095 with I 2 3s(I).

Hydrogen

CAD4

(0.80 + 0.35 tana);

time

Headspace

were obtatned a

MO Ka radiation,

exposure

collected;

on

lattace constants

o-scan

vaponxataon inspected

of the 1 3 C NMR spectra.

analyses

For data collection

inlet

and were satifactory.

mounted

monochmmatrzed

from

standard.

were obtained

compounds

X-ray

scans,

products.

for each product.

were

direct

impact

(%) are reported

difficulty

measuring

solutions

of gaseous

Elemental analyses

mm

the

NMR data

tetramethylsllane practical

punty.

to the electron

for the detection

intensrty

sample

over

pnor

During

recording.

the full recordmg was carefully

check

vapours

gaschromatograph

were obtsnned from a Finnegan MAT 1020 with

located

at calculated

positions.

reflections

4537

unique

monitored reflections

every were

with MULTAN 8022 m default

R = 0.059 for 1095 observed Atomrc scattering

factors

data. were

G. VERARDO et al

10626

taken from Cromer & Mann.24

Table 5.

Crystal

Data

Formula

/mn

0.2

x 0 2 x 0.5

p2,/c

h range

a/A

7.259(3)

k range

0.32

b/A

27.466(2)

1 range

0 14

c/A

12.525(2)

scan

B/”

99.23(3)

Measd.

Group

D ..,,fg

cmm3

~(Mo

Ka)A

p/cm-’ F(OO0)

anhydrous

added

ethanol

sohd

of

2402

Structure

MuLTAN80

R factor

0.058

0.71069

Final

R,

0.059

0.86

Room temperature

for

the

Headspace

analyw over

GC-MS. The

of

SHELX76

factor

Preparation

was performed the reactron

procedure

above reactin

Reaction

between

out according

was the

substrate

after

the additin

result

of &,

of ethanol

study

ca

10% yield

product.

(l7)

described

of &

and

(ca.

50

efficient

19 evolved of

solvent.

by sampling

and analysrng

the

It by or

not

lower yields

of

the

variatxon

of

a

(Table 6) 2.

The react&on was

for the preparation

was obhned;

the

by addition

of the ~~taal reagents

the

of

the addltin

chltide

6 m substantially of

of

from a sortable

when & was used as a substrate

to the optamal procedure

bexng the other observed

hydrogen

of addition

products the

ether

at rcom temperature

N,N’-Diarylaminomethane

only

the end

IZI recrystallized

order

yielded

suspension

A

m the case of the syntheu

IS IJI part

parameters,

wUe

is completed

by filtratin,

with inverted

procedure

10 nunutes after

at O°C slowly,

mxture

using ethanol to end the process

ga_k.

(5, 30 mmol) kept at O°C under

About

The preupltatin separated

of

(l, 10 mmol) III anhydrous

chlonde

Argon.

(30 ml) EI added

separates.

atmosphere

of

Reflections

28

Final

to neat oxalyl

The preupltate,

number

0 -

1.36

in an atmosphere

The

mode

Ref lnement

1,3,5-trxarylhexahydro-1,3,5-triazine

ml) was slowly

ether.

-8.8

8

Procedure

appropriate

a

3.26

1024

General

stxnng

/”

Solution

2464.6(6)

z

(&)

size

Cryst.

0 range

v/A3

carned

Details

252.3

Space

G

Experimental

C15H1202N2

M W.

and

and

of 6. When

N,N’-dlphenyloxalanude

Hetcrocyclesfromhetcxocycles

10627

A slrmlarresult was obtained when N,N'-&(4-r&.rophenyl)armnomethane (E)

was

used, but the cyclicproduct &I was not presentat all. Table 6 mol

z/m01

&

Reaction

Quenching

Reaction

Yield

time

reagent’

solvent=

(W

6

10 min

Et,Ob

-_

5oc

3

10 min

EtDH

__

40o

12

10 min

EtQH

-_

2Sd

1

10 min

EtCtl

Et,0

45

3

10 min

EtDH

Et,0

75=

6

10 min

EtDH

Et,0

58

3

10 min

EtDH

3

10 mln

EtDH

6

16

EtCH

hours

Dioxane

mixe

CHCl s

mixP

Hexane

65

‘Anhydrous materials were used. bComnercial diethyl ether was used as received ‘DI-MS analysis of mother liquors obtained after filtration of & showed the presence of N,N’-diphenyloxamlde [l&q MS (m/z): 240 (M@, 43), 121(30), 120(31). 105(12), 93(100), 92(22). 77(58)] dDI-MS analysis of mother liquours obtained after filtration of & showed the presence of 14a and bis(N-ethoxyoxalyl-N-phcnyl)diaminomethane [MS (m/e)* 398(