S Y N T H E S I S OF B I F U N C T I O N A L O R G A N O P H O S P H O R U S C O M P O U N D S

1. ADDITION OF PHENYLPHOSPHINE TO UNSATURATED COMPOUNDS

B. A. A r b u z o v , G. M. V i n o k u r o v a , a n d I. A. A l e k s a n d r o v

Chemical Institute, Kazan' Branch, Academy of Sciences of the USSR Translated from Izvestiya A kademii Nauk SSSR, Otdelenie Khimicheskikh Nauk, No. 2, pp. 290-295, February, 1962 Original article submitted July 14, 1961

The addition of primary phosphines to unsaturated compounds has not yet been investigated systematically, and in the chemical literature there is information only about the cyanoethylatfon of phenylphosphine [1-2]. It is, however, quite clear that the addition of primary phosphines to unsaturated compounds containing the func- tional groups NHz, COOH, OH, CH2C1, etc., is of great interest both from the point of view of the development of methods for the synthesis of organophosphorus compounds, and from the point of view of their practical applica- tion in the synthesis of polyesters and polyamides.

In a previous paper [3], we described the addition of phenylphosphine to methacrylic esters, methyl acryl- ate, and allyl alcohol. It was shown that phenylphosphine adds both to esters of acrylic and methacrylic acids and to allyl alcohol with formation of bifunctional compounds in 50-70% yield. In continuation of the study of the addition of phenylphosphine to unsaturated compounds we have carried out the addition of phenylphosphine to allylamfne, allyl acetate, and 5-vinyl-2-picoline, and we also carried out the oxidation of all the addition products synthesized.

The addition of phenylphosphine to allylamine, allyl acetate, and 5-vinyl-2-picoline was carried out by heating the reactants together in absence of catalyst or in presence of azodiisobutyronitrile. The experiments showed that phenylphosphine adds to 5-vinyl-2-picoline fairly readily in absence of catalyst (with formation of the addition product in 50% yield), and with much greater difficulty to allylamine and allyl acetate. The use of a catalyst in the addition of phenylphosphine to allylamine and allyl acetate enabled us to increase the yield of products to 60% or even 80% (Table 1). We showed, therefore, that the addition of phenylphosphine to allyl de- rivatives goes readily in presence of a catalyst producing free radicals.

The resulting tertiary phosphines readily undergo addition with oxygen and sulfur. The phosphine oxides and sulfides formed are either thick, immobile, colorless, or feebly yellow liquids having a weak, unpleasant odor (Nos. 1-6,10 in Table 2~ Nos. 1-7 in Table 3), or crystalline solids (Nos. 7,8,9,11 in Table 2~ Nos. 8-11 in Table 3).

We met some difficulties in the calculation of the molecular refractions of phosphine oxides and sulfides obtained from the products of the addition of phenylphosphine to methacrylic esters and allylamine. According to an investigation by Kosolapoff [4], the atomic refraction of phosphorus in phosphine oxides containing simple alkyl groups is 5.5. For our compounds, apart from Nos~2 in Table 3, this value for the atomic refraction of phosphorus does not fit. According to our calculations, the value of the atomic refraction of phosphorus in our tertiary phosphine oxides and sulfides varies in the range 5.69-6.33 (see Tables 2 and 3) and, if we take the mean value, is 6.02 with maximum departures of +0.32 and -0.26.

E X P E R I M E N T A L

A dditio n of Phenylphosphine to A llylamine, A 11yi Acetate, and 5- Vinyl- 2-picoline. A four- necked flask fitted with stirrer, reflux condenser, thermometer, and tube for the passage of nitrogen was charged with 9.8 g of phenylphosphine, 12 g of allylamine, and 0.4 g of azidiisobutyronitrile. The reaction mixture was cautiously heated to 140-150 ~ and kept at this temperature with stirring for 10 hr. Volatile substances were drawn off under suction, and the residue was fractionated. As a result of the fractionation we obtained 15.7 g (78.8%) of bis(3- aminopropyl)phenylphosphine~ b.p. 148.5-149 ~ (1 mm)~ n2~ 1.5740, d2~ 4 1.0336. Found- C 64.18~ H 9.47; P 13.89%~, MR 71.5. Cl~H21PN 2 [-----3. Calculated: C 64.28~ H 9.37~ P 13.83% MR 71.10.

267

r-q

LU

rr~

b~

OO t.~ r162

O r

e ~- ~ - ~

r -.~

r )

t

The addition to allyl acetate and to 5-vinyl-2-picoline was carried out analogously. For the constants of the addition products, see Table 1.

Preparation of Phosphine Oxides. Tertiary phosphine oxides were prepared in two ways: 1) by oxidation with oxygen, and 2) by oxidation with hydrogen peroxide by the method of [2]. Oxidation with oxygen was effected by passage of gaseous oxygen through the substance at 130-140 ~ for 10-15 hr, and subsequent vacuum fraction of the oxidation product. In this way, from 13.6 g of bis(3-aminopropyl)phenylphosphine we obtained 6.5 g (44.9%0) of the phosphine oxide; b.p. 179-181" (1 mm)I n2~ 1.5660; d2~ 4 1.1208. Found: C 60.12; H 8.87; P 12.60%~ MR 69.93. CItH21PN 2]_~s. Calculated: C 60; H 8.753 P 12.91%~ MR 70.12. In an analogous way we synthesized Nos. 1, 2, 4-6 in Table 3.

Oxidation with hydrogen peroxide was carried out as fol- lows. A solution of 14.8 g of bis[2-(methoxycarbonyl)ethyl]- phenylphosphine in 18 ml of acetic acid was warmed to 60 ~ and 5.9 g of a 30%0 solution of hydrogen peroxide was added. The reaction mixture was then heated, first at 75%0 for 15 rain, and then at 100" for a further 15 rain. Fractionation then gave 11,9 g (76%) of bis[2-(methoxycarbonyl)ethyl]phenylphosphine oxide; b.p. 201-203" (2 mm); m.p. 71-71.5 ~ Found: C 86.26; P 10.331 H 6.6%0, Ct4H~gOsP. Calculated: C 56.373 P 10.41 H 6.37%o. Bis[2-(propoxycarbonyl)ethyl]phenylphosphine oxide, bis(3-acetoxypropyl)phenylphosphine oxide, and bis[2-(6- methyl-2-pyridyl)ethyl]phenylphosphine oxide were prepared analogously (see Nos. 3, 7, 8, and 9 in Table 3).

Preparation of Phosphine Sulfides. All the phosphine sulfides were synthesized by the addition of the calculated amount of sulfur to the corresponding tertiary phosphines. The synthesis of bis(3-hydroxypropyl)phenylphosphine sulfide can be taken as example. Sulfur (1.16 g) was sprinkled into bis- (3-hydroxypropyl)phenylphosphine (8.2 g)3 rise in temperature to 29* was observed. The reaction mixture was heated at 150" until the sulfur disappeared (4 hr). On cooling, the con- tents of the flask solidified. We obtained 9 g (86.7%0) of a product of m.p. 101-102*. After recrystallization from benz- ene the melting point of the product became 102-103.5". Found: C 56.321 H 7.51; P 12.02. ClzH19PS. Calculated: C 55.81; H 7.361 P 12.01~

Preparation of Bis(2-carboxyethyl)phenylphosph!n e Oxide. Bis(2-carboxyethyl)phenylphosphine oxide was pre- pared by the hydrolysis of the corresponding methyl ester with dilute hydrochloric acid. From 2.3 g of bis[2-(methoxycar ~ bonyl)ethyl]phenylphosphine oxide we obtained 1.5 g (75%) of recrystallized (isopropyl alcohol) bis(2-carboxyethyl)phenyl- phosphine oxide, m.p, 199-202". *

*Bis(2-carboxyethyl)phenylphosphine oxide was first prepared by the hydrolysis of bis(2-cyanoethyl)phenylphosphine [2].

268

TA

BL

E 2

No.

t0

tt

For

mul

a B

.p.

in ~

fp

in m

m)

CH

a I

CeH

sP (C

H2

--C

HC

00C

H3)

2 JJ S

CH

a t

C,HsP

(CH

a--C

I:IC

O 0C

.~H5)

2 H S

CH

~ I

C~H

sP (C

H2-

-CH

C00

CaH

02

IF s

CH

a I

C,H

6P (C

H._

--CH

CO

OC

aHT-

I)~

S

CHa

C,I

IsP (CH2--~HCOOC4H.),

II

S

C, H

sP

CH

a !

(CH

,--C

HC

O 0C

4F[~

-i)2

C,H~P (CH~CH,COOCHs),

* II S

C.tI

sP (C

H2C

H2C

H20

H) *

* IL S

C,H

~P (C

HaC

H2C

H2N

H2)

z ***

C,Hs

P (C

HaCH

aCK~

0COC

Ha)a

II S

C~Hs

P (CII ~C

H~--

~--C

Ha)~

****

II S

N

~84 (0,3)

194-

-195

(1,

5)

t95

--i9

6 (

0,5)

188-

-189

(0

,5)

20

8--

2ti

(0,

5)

191,

5--1

92 (

i)

200-

-201

(t)

M

.p.

52--

54 ~

M.p

. 10

2--1

03,5

~

199-

-t99

,5 (

1) o

M

.p.

41--42

227

(t)

M.p

. lt

a ~

~ 20

n

D

Fou

nd,

%

Calc

u..

%

~RD

i,t7

03

1,14

38

i,09

97

1,09

97

1,07

89

t,07

02

t,17

54

t,54

78

1,5.403

1,52

58

1,52

42

1,52

~9

1,5i

75

t,54

94

C 5

6,35

P

9,49

P

6,83

P 8,

43

P 7,

76

P 7,

89

C 6

2,00

P

8,38

H

7,2

8

P 7,

16

C 5

3,5

P 9,

87

tI 6

,06

C 5

6,25

P

12,0

2 H

7,

51

P 12

,06

t2,0

1 12

,43

I2,5

8 P

9,46

P 8.

26

C 56

,4i

P 9,

33

H 6

,76

P 8,

37

P 7,

78

P 7,

79

C 6

t,9

9

P 8,

27

H 7

,28

P 7,

28

C 5

3,46

P

9,56

H

6,0

2

C 5

5,81

P

12,0

1 H

7,

36

P i2

,10

S 12

,50

P 9,

48

P 8

,t5

92,9

3

101,

66

tlt,

28

tt0

,9t

t20,

54

t20,

67

92,7

0

Foun

d AR

D

6,33

5,83

6,2

t

5,85

6,23

6,20

6,t

i

Yie

ld,

73,3

83,5

85,2

80,7

75,3

73,4

91

96,7

66~6

66,1

" 62

,2 %

0

TA

BLE 3

No.

3 4 5 6 7 8 9 10

tt

For

mul

a

CH

2 i

C,H

,P (C

H~C

HCO

OCH

~)~

U

O

CH

,

C,Hs

P (C

H2--

CHCO

OC2H

I) ,

II

0 C

rl~

C,It

, P "

(CH

,~II

CO

OC

~H,h

CtI8

C.H

,P (

CH

=~H

CO

OC

,H.-i

h

CIt=

CtH

sP (C

Hz~

HC

OO

C,II

,)~

C,H

sP (C

II2C

II2C

H~N

H,h

II O

C,H

mP (

CH

,CH

zOC

OC

H,h

[I o

C. H

~[P (

CH

~CH

, OC

H,)

, "

0 N

C

,HsP

(CH

~CH

zC00

CH

sh **

II o

C.H

~P (C

H,C

HzC

H,0

H),

***

11 0

C,H

IP (C

H,C

H~C

OO

Hh

****

II O

B.p

. in

*c

(p

in r

am)

19t,

5--t

92 (

1,5)

t96

,5--

t98

(t,

5)

t97-

-i98

(1)

2i0-

-211

(1,

5)

209-

-210

(l)

179~

180

(1)

223-

-224

(i)

M.p

. 84

--85

~

201-

-203

(2)

M

.p.

7t-

-7i,

5 ~

22

0--2

23

M.p

. 77

--78

~

M.p

. i9

9--2

02 ~

1,t6

64

t,i2

76

t,08

63

t,06

27

t,06

80

1,12

08

t,t6

t7

20

nD

i,51

78

1,50

79

i ,50

06

t,49

56

t,49

87

t,56

60

1,51

78

B

Fou

nd

C 5

8,70

P

9,43

H

7,

16

C 6

0,95

P

8,42

H

7,

65

C 6

2,6

P 8,

00

H

8,t

9

P 7,

8i

P 7

,35

C60

,12

P t2

,60

H

8,87

P

9,72

P 8

,62

C 5

6,26

P

I0

,33

H 6

,6

C 6

0,08

P

i2,5

H

8

,i0

% Calcu.

C 5

8,90

P

9,45

H

7,

13

C 6

i,05

P

8,68

H

7,

68

C 6

2,6i

P

8,09

H

8

,i4

P 7

,56

P 7

,56

C60

,00

P 1

2,91

H

8,7

5

P 9

,45

P 8

,52

G 5

6,37

P

I0,4

H

6,3

7

c 5

9;5

P 1

2,8

H

7,8

5

Found

MR

D

84,7

9

93,7

6

i03,

70

i12,

75

i12,

79

69,9

3

85

AR

D

5,69

5,4

3

6,i

2

5,93

5,9

8

5,76

6,i6

Yield, %

54

,2

6i,9

52,8

79,7

81,8

44,9

81,0

58,7

76,2

-21 75

* Rec

ryst

alli

zed

from

hep

tane

. *

* R

ecry

stal

lize

d fr

om e

ther

. *

* *

The

pro

duct

was

fra

ctio

nate

d,

and

the

crys

tall

ine

part

was

sep

arat

ed a

nd w

ashe

d w

ith

ethe

r.

* *

* * R

ecry

stal

lize

d fr

om i

sopr

opyl

alc

ohol

.

SUMMARY

1. The addition of phenylphosphine to allylamine, allyl acetate, and 5-vinyl-2-picoline was carried out,

2. ~Ibc addition of phenylphosphine to allyl derivatives proceeds readily under the catalytic action of azo- diisobutyronitrile.

3. Tertiary phosphine oxides and sulfides containing two functional groups were prepared.

4. By the hydrolysis of bis[2-(methoxycarbonyl)ethyl]phenylphosphine oxide the corresponding dicarboxylic acid was prepared.

1.

2. 3. 4.

L I T E R A T U R E C I T E D

F. G. Mann and Yan J. Miller, J. Chem. Soc. 1952, 4453. M. M. Kaechut, ]. Hechenbleikner et al., L Am. Chem. Soc. 81, 1103 (1959). B. A. Arbuzov, G. M. Vinokurova, and I. A. Perfil 'eva, Dokl. AN SSSR 127, No. 6 G. M. Kosolapoff and R. F. Struck, Proc. Chem. Soc. (October, 1960).

All abbreviations of periodicals in the above bibliography are letter-by-letter transliter-

ations of the abbreviations as given in the original Russian journal. Some or all of this per/-

odical l i terature may well be ava i lab le in Engl ish translation. A complete l is t of the cover - to - cover Engl ish t ranslat ions appears at the back of this issue.

271