The reaction of 2-trifluoromethyl-3,3-difluorooxaziridine with nucleophiles.

JournalofFIuorineChemistry, 14(1979)289-297 OElsevier SequoiaS.A.,Lausanne -F'rintedinthe Netherlands

289

Received: April3,1979

THE KEACTION

OF 2-TRIFLUOROI+ETUYL-3.3-DIFLUOROOKAZIRIDI1X

WITH

KUCI,EOPHILES.

AKIRA

SKKIYA

Department 66506,

and DARRYL

D. DESPIARTEAUl

of Chemistry,

Kansas

State University,

Manhattan,

Kansas

USA.

SUMMARY The facile nucleophiles

of CF3NT

-t CF3N(Nu)C(O)F

+ Nu-

with alcohols,

NaN3 and NaOCN were

carhoxylic

carried

nnd the expected

compounds

of CF N(Nu)C(O)F 3

with

forming

with a variety

of non-fluorinated

are discussed.

CF3q Reactions

reactions

CF3N(Nu)C(0)Nu.

and the novel

amine

characterization

acids, mercaptans,

amines,

KSCN, KCN,

All except NaN3 and NaOCM were.reactive

out. were

+ F-

isolated

additional

in most

nucleophile

With CH3C02H,

cases.

was observed

in many

the latter reaction Ten new compounds

CF3N(H)OC(0)CHi.

Subsequent

by IR, NMR and physical

reaction cases

forms CH3C(0)F

are reported

with

properties.

INTRODUCTION The novel with

fluorinated

These reactions CF3C!,

CF3Nz2%,

oxaziridine,2 nucleophilcs are analogous

and thus reaction

respectively.

With CF30-,

with

has been shown to undergo

attack

occurring

to those observed with

fluoride

CF3N(OCF3)C(0)F

exclusively

reactions at nitrogen. 3,4

with hexafluoropropene

forms CF3NFC(0)F

epoxide,5

and CF3CF2C(0)F,

and CF3CF(OCF3)C(0)F

are the

290

products.

In general,

the reactivity

CF3CFCF2i) with fluorinated philes

nucleophiles.

are less nucleophilic

CF3NT

would

CF3NTO or CF3Nq

philes

leads

at other

of the oxaziridine to many

with

might

interesting

fluorinated

analogs,

the latter.

nucleo-

we expected

In addition,

that at-

+ F-

with a variety

of non-fluorinated

new compounds,

but no evidence

Ten new compounds

than nitrogen.

highly

be observed.

-f CF N(Nu)C(O)F 30 + -f CF3NCFMu

+ Nu-

Reaction

Because

reactivity

than nitrogen

+ Nu-

is lower than that of

than their hydrocarbon

show increased

tack at a site other

of CF3NT

are reported

nucleo-

for attack

and chacterized.

EXPERIMENTAL All volatile

General. vacuum

systems

was carried

as previously

except

Liquids

were distilled

dynamic

vacuum.

of new compounds

2

CF3NT

before

Characterization

were

obtained

from commercial

sources.

use and solids were dried by warming

The oxaziridine

steel

was prepared

and purified

under

by the literature

of CF3hq

Reactions

were

less steel valve.

condensed

carried

out in 1Oml Kel-F reactors

Solid reactants Thr

for S--l2 hours.

flask

described.

in glass and stainless

2

Reactions

wer-c

were manipulated

out in the usual way.

All chemicals

method.

compounds

reactor

in by vacuum

was

fitted with a stain-

were added and pumped then

coole~l

transfer.

to

-193”

The reactor

rL!ld volat.

warmed

appropriate

time.

The reactor

gases were

checked.

Volatile

directly

products

were

vacuum

rr~;lrtn:lts

in a Dewar

to warm slowly

to 22' and allowed

was then cooled

ilc

was tllen placed

filled with s 500 ml of CFC13 at -110" and allowed

over a 16 hour period.or

under dynamic

to 2.2"

to stand for an

to -193" and non-condensable

then separated

by glc or distil-

291

lation through traps cooled to appropriate temperatures. Details for all reactions are summarized in Table 1.

Characterization for new compounds

follows. CF3N(OCII3)C(O)F: b.p. 60.4O; mol. wt. 165.1, calcd. 161.06 = 6.64 kcal/mol; log P(torr) = 5.126 - 45.50 - 2346 x lo*; AH vap T T2 = 19.9 eu; IR 3030 (VW), 3000(w), 2968(m), 1871(vs), 1788(w), 1468(w), AS vap 1449(w), 1395(w), 1310(m), 1275(vs), 1253(vs), 1205(vs), 1155(vw), 1097(s), 1022(m), 1001(s), 979(m), 789(w), 757(m), 693(s) cm-';NXR 4" 65.4, d, CF3; 11.5, q, C(O)F; 6 4.7, s, CH3; JFF = 14.4Hz. CF3NFC(0)OCH3: m.p. -71.5 to -70.8"; mol. wt. 157.0, calcd. 161.06; IR 2963(m), 286O(vw), 1852(vw), 1818(m), 1803(s), 1555(vw), 1445(m), 1307(vs), 128O(vs), 1245(vw), 1214(vs), 1192(sh), 1098(sh), 1070(m), 1041(m), 1009(w), 932(w), 823(m), 813(m), 781(w), 719(m) cm-l; MMR $k 68.1, d, CF3; 75.0, q, vr; 6 4.2, s, CH3; JFF = 11.2 Hz. CF3N(OCH3)C(0)OCH3; b.p. 97.5"; mol. wt. 173.0, calcd. 173.09; log P(torr) = 3.338 + 1697 - 6919 x 102; T T2 AH = 9.32 kcal/mole; AS = 25.1 e.u.; III 304O(vw), 3001(w), 2997(m), vap vap 2915(w), 2860(vw), 2835(vw), 185O(vw), 1788(vs), 1510(w), 146O(vw), 1442(m), 131S(vs), 1298(vs), 1057(x), 1197(vs), 1113(m), 1062(s), 997(m), 932(m), 901(w), 862(vw), 814(m), 773(m), 722(m), 642(m), 601(m) cm-l; m.

9" 65.4,

s, CF3; 6 4.2, br, NOCH3; 4.3, s, COCH3. CF3N(OC2H5)C(0)F: m.p. -58.5 to -58.0"; mol. wt. 170.0, calcd. 175.08;IR2992(m) 2957(w), 2910(w),

1860(x), 1395(w), 1309(s), 1283(s), 1255(vs),

1206(=),

1120(~), lllO(v~), 1084(s), 1017(s), 987(s), 876(w), 795(w), 754(m), 606(w) -1 cm ; mm $” 65.1, d, CF3; 11.25, q, C(O)F; 6 4.4, q, 'X2; 1.5, t, CH3; = 15.0, JHH = 7.3 Hz. JFF CF3N[OCH(CH3)2]C(0)F: m.p. - 72.3 to -71.6O, mol. wt. 190.3, calcd. 189.11; IK 2997(m), 2951(w),2278(vw), 1968(vw), 1867(~~), 1845(sh), 1500(m), 1473(w), 138~(~), 1339(sh), 1310(s), 1264(vs), 1208(vs), 1150(m), 1113(m), 1082(s),

292

1043(w), 1018(m), 985(s), 95o(vw), 911(m), 830(w), 794(w), 745(m), 698(m), -1

612(w) cm

; mm $“’ 64.3, d, CF3; 9.65, q, C(O)F; 6 4.5, Sept., CH; 1.5,

d, CH3; JFF = 15.3, JIiH = 6.2 l?z.

CF3N[OC(CH3)3lC(O)F: m.p, -55.3 to -54.5"; mol. wt. 204.0, calcd. 203.14; 1~ 2982(m), 1877(vs), 1857(s), 1836(sh), 1495(m), 1368(w), J-346(~),1303(s)9 1252(s), 1209(n), 1145(vw), 1070(m), 1009(m), 977(m), 949(w), 892(vw), 851(w), 805(w), 733(vw), 698(w), 600(w) cm-l; m q, C(O)F; 6 1.54, s, ~3; CF3N[OC(0)CH3]C(O)F:

JFF = 16.4 r-1~.

t~.~. -58.0

1878(vs),

1843(x),

1795(w),

1211(vs),

1170(x),

uoo(vs),

740(vw),

722(m),

688(m),

q, C(O)F;

14.5,

$" 62.4, d, CF3; 7.90,

to -57.1';

1442(w),

1370(w),

1033(s),

645(w),

mol. wt. 186.5, 134O(vs),

1000(S), 895(w),

585(m),

521(m)

cm-l; WR

m.p. 35.8 to 36.0'; mol. wt. 145.4,

3223(m),

1876(w),

1856(m),

1374(m),

1358

(S),

954(s),

g%(w),

568(w)

cm

-1

189.07;

1313(s),

IR

1272(Vs),

SOl(v’i~) >

832(m),

O* 63.0,

d, CF3;

6 2.6, s, CH3; JFF = 14.Oliz.

CF31J(H)OC(0)CH3:

1447

chlcd.

(W),

870(m),

calcd.

143.07;

IR 3250(m)

1788(vs),

1732(vw),

1692(vw),

1512(w),

1500(w),

1312(VS),

ms(VS),

1172(VS),

1103(W),

10'~4(S),

823(m),

; mu $” 70.5,

769(vw),

680(sh),

714(w),

d, CF3; 15 8.5,

br, NH;

664(m),

2.4, s, CH3;

600(~.~)> JHF =

8.8 Hz. CF3N(sC2H5)C(0)F:

m.p.,

2953(w),

1695(vs),

915(vw),

884(m),

2.60,

q, C(O)F;

CF3N(CN)C(0)F:

125O(vs),

842(w)

674(s),

li84(s),

620(w),

1223(vs),

1208(sh),

1810(w),

1794(m),

1069(m), 1012(w),

755(w),

n, CF3; 14.0, br, C(O)F.

705(sh),

calcd.

1116(m),

464(m)

cm

-1

191.48;

IR 2985(w).

IO6O(v~~), 976(vw)>

;~pz_ I$*53.9, d, CF3;

t, CH3; JFF = 10.9, JHH = 7.2 Hz.

b.p. 42'; mol. wt. 156.5,

1872(s),

788(vw),

1223(x),

6 2.93, q, CH2; 1.60,

1881(x),

844(w),

glass -193", mol. wt. 195.0,

calcd.

1767(s), 995(w),

674(m),

156.04;

1616(vw), 988(m),

601(m),

IR 2237(m), 1435(vS),

937(w),

501.(w) cm-+;

1902(s),

129O(vs),

912h),

s6OCw)t

IjT@ 9" 68.1,

293

Table 1

Reactions of CF3q

Nu-(Nu/CF~NCF~~)~

with Nucleophiles

Conditions Hr. "C

Product(c)(Yield%)

CH30H (l/l)

-111 to 22"

16

CF3N(OCH3)C(O)F (80)d

CH3OH (Z/l)

-111 to 22"

16

CF3N(OCH3)C(O)OCH3 (90)e

CH30H (l/l>b

-111 to 22O

16

CF3NFC(O)OCH3 (99)d

C2H5OH (1/l)

-111 to 22"

16

CF3N(OC2H5)C(0)F (8Ud

(CH3)2CHOH (l/l)

-111 to 22"

16

CF3N[OCH(CH3)2C(0)F (8S)e

(CH3)3COH (l/l)

-111 to 22"

16

CP3N[OC(CB3)3]C(O)F (93)e

CH3C02H (l/l)

22"

4.5

CF3N[OC(O)CH3]C(O)F (32)d CF3N(H)OC(0)CH3 (21)d CH3C(O)F (46)h

CH3C02H (2/l)

22O

4.5

CF3N[OC(0)CH3]C(O)F (Il)d CF3N(H)OC(0)CH3 (75)d CH3C(0)F (64)h

CII3CH2SH(l/l)

-111 to 22O

1G

CF3N(SC2H5)C(b)F (30)f

KCN (lOO/l)c

22O

48

CF3N(CN)C(O)F (40)d

KSCN (lo/l)'

22"

22

CF3NC0 (SC)'

a.

All reactions with 1.0 mm01 of CF3Nq

where noted. b. 1.0 mm01 of CF3NFC(0)F C.

No

d.

Isolated by glc.

xar.

e.

-111' trap after a -35" trap.

f.

-74" trap.

8.

-193' trap after a -111" trap.

h.

-111" trap after -78" trap.

and 5.0 mm01 of HaF except

294

RESULTS

AND DISCUSSION

The reaction

of CF3NT

pected

to occur readily.

alkoxy

nucleophile

products,

and reaction

with HF and several

reaction

Methanol

was chosen

with CF3q

low molecular

as a typical Produced

III

CH30H HF + [2] <-VF

We believe reactions

that

III-VI,

NaF to absorb reactions

HF

III-VI,

CH30H

1

the following

reaction and

[2] arise from reactions

141 (99%) was observed.

these potential [2].

reaction

the same conditions

yield

reactions

the oxaziridine uncatalyzed

forms

I is catalyzed to form

leads

reaction,

CF3NT

in an effective the formation

unimportant

CH30H

reactionof

are effectively low molecular

is consumed

increase

[l] with CH30H

These results attack

suggest

first The in-

by NaF and the fact that side

eliminated. weight

Reaction

products

of HF with

and thus in the

by both CH30H and HF.

in CH30H relative

of [2] via II.

for

in the presence

[2] is formed via path II.

from base catalysis

to several CF3NT

with

[2] in very high yield.

[l] and that

oj

NaF does not inhibit

paths are clearly

of CF3qC

To eliminate

out in the presence

by NaF and that the nucleophilic

of [l] follows

of HF with

Reaction

Assuming

[l] in very high yield and subsequent

at nitrogen

I and II.

of [3] with CH30H was carried

of NaF yields

that reaction

131

[A] or [l] + HF

of [l] and

favors

are possible

V 1 CH30H

CF3NFC(0)OCH3

[l] and

CF3NFC(0)F

the formation

results

[Z] (30%) along

in several ways as shownby

CH30H v

CF3Nq

II 1 CH30H

creased

two CH30 containing

scheme.

CH30H

occurs

was ex-

source of an

Four products

wt. products.

and could arise

HF + [I] 7

under

nucleophiles

[I] (35%) and CF3N(OCH3)C(0)OCH3

CF3N(OCH3)C(O)F

from this reaction

with oxygen-containing

The latter

to the oxaziridine

and

295

Other

alcohols

The selectivity

CF3N(OR)C(O)F. in the order as

react similarly

to CH3011 i.n the presence

for the formation

lo < 2" < 3O alcohols.

the size of OR increases.

for a wide variety Reaction

d-' of CF3.XF20

with acetic

expected

product,

CF3N[OC(0)C~~3]C(O)F

expected

product,

CF3N(H)OC(0)CH3

and unreacted

oxaziridine.

2:l scalegave

[6]asthe

These

can be explained

results

CF3fiFT

major

+ CH3C02H

+ co

In support

+---

2

of this, reaction

and CO2 in excellent

amount

under

the same conditions

reaction

on a

in equal amounts.

scheme.

CH3C02H/NaF

~CP3??[0C(0)CH3]C(O)OH}

+ CH3C(0)F

of [5] with H20 in the presence

of NaF forms

[61

yield.

I51 + Hz0 s

{CF3N[OC(O)CH3]C(C)OH]

L

+ HF

isI

A related reaction of C2F5C(O)F with RC02H is also supportive scheme.

of an un-

+HF

1

l6J

of NaF led to the

along with CO2, CH3C(0)F

with CO2 and CH3C(0)F

by the following

[5]

were not tried.

[5], hut a significant

product

=

1 and II are general

acid in the presence

of CH3C02H

increases

II is less favorable

examples

[6], was observed

Reaction

path

reactions

but additional

of alcohols,

of the latter

Thus reaction

Most probably,

of NaF to form

In this case,

reaction

occurs

to give RC(O)F

of this

and the stable acid

C2F5C02K. ‘7 Two sulfur nucleophiles, W-ith ethanethiol, in moderate the reaction

yield.

C2H5SH

the expected

and KSCN, were

product

CF3N(SC2H5)C(0)F

With KSCN, none of the expected

provided

a high yield

tried with

synthesis

[i'] could be isolated

product

of CF3NC0

CF3Nq.

was found.

Instez

from the oxaziridine.

296

We believe

that further

is especially following

facilein

reaction

of CF3N(Nu)C(O)F

these cases

with

and the products

the sulfur

nucleophjle

can be explained

by the

reactions. + C2115SIi

CF3&??$

z

171 + HF

1 C2H5SH/NaF CF3NCO

+ (C2H5S)2

CF3Nq

+ KSCN

f--

(CF3N(SC2H~C(O)SC2h5}

A

{CF3N(SCN)C(O)F)

Neither

consistent observed

with with

reflects

yellow

Attempts

to react

products.

Similar

potential

CF3&$

of products

reaction

with

CF3hq.

anine

of a carbon

The reaction

(40%) could be isolated CF3N(F)C(0)F,

results

results

of sulfur

(C2A5)2NH

after

nucleophiles

b

+

KCN

were unsuccessful.

in the presence

excess

of the ?JaF gave

two days at 22".

4

CF3N(F)C(O)F

CF$CN)C(O)F

unsuccessful.

yield

The other

of the oxaziridine

+ KF

Previously, 4

KCN was all.owed to react

was slow but a significant

from isomerization

simply

in these compounds.

the reaction.

CF3q

identified.4

sulfur nucleophiles

(CF3)2NH was similarly

nucleophile,

reactions,

were previously

but no CF N[N(C H ) ]C(O)F was observed. 3 252

the very acidic

As an example

in the respective

with

with nitrogen and

but a low volatile

(CF3S)2 was clearly

disproportionation

from Nat13 was unreactive

a variety

identified

observed

CF SH and in this case, 3

the low oxidation

+ KF

solid were

the proposed

the observed

Apparently,

with

{CP3N(SCN)C(O)SCN}

(C2H5S)2, nor (SCN)2 was unequivocally

oil and non-volatile

Aside

c--

+ KP

KSCN

1 + CF3NCO

(SCNh

+ CF

of CF3N(CN)C(0)F

product, by KF formed

in

297

to prepare

Attempts ful.

CF3N(OH)C(O)F

It was hoped

However,

from NaOH and the oxaziridine

that this compound

the reaction

was very

might

yield

fast to yield

were unsuccess-

CF3Nm

by loss of HF.

CO2 as the main

identifiable

product. Characterization properties further

are not aware

the utility

of any analogous

methods

of synthesis

of this novel

come readily

described

can be obtained

from CF N(R)c(o)F 3

of such compounds

1 H and lgF NMR

in this work

formed

oxaziridine

N-trifluoromethyl

CF3N(l?)OC(O)CH3

variety

by

The new materials

was straightforward.

illustrate

alternate

of all new compounds

from CF3q in synthesis.

derivatives,

to mind.

suggests

We

nor do any

The synthesis

that many analogous

by hydrolysis.

obtained

2 IR and physical

of amines

A study of this reaction

from the nucleophilic

attack

with

on CF,lT

is underway.

ACKNOWLEDGEMENT The support DAAG29-77-G-0071)

of this work by the Army Research is gratefully

Office-Durham

(Grant No.

acknowledged.

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Alfred

2

E. R. Falardeau

3

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A. Sekiya

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5

P. Tarrant,

C. G. Allison,

Chem. Rev.,

5, 177 (1971).

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P. Sloan Fellow,

7

and D. D. DesMarteau,

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1975-77.

Akad.

and N. Ishikawa,

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g,

(Japan),

3529

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and E. C. Stump,

V. A. Ginsburg,

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K. P. Barthold

S. P. Markarov,

Doklady

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and