Synthesis of bifunctional organophosphorus compounds

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  • SYNTHESIS OF B IFUNCTIONAL ORGANOPHOSPHORUS COMPOUNDS

    1. ADDITION OF PHENYLPHOSPHINE TO UNSATURATED COMPOUNDS

    B. A. Arbuzov , G. M. V inokurova , and I. A. A leksandrov

    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.

    EXPERIMENTAL

    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

  • TABLE

    2

    No

    .

    t0

    tt

    Fo

    rmu

    la

    B.p

    . in

    ~

    fp

    in

    mm

    )

    CH

    a I

    CeH

    sP (C

    H2 --

    CH

    C00C

    H3)2

    JJ S

    CH

    a t

    C,H

    sP (C

    Ha-

    -CI:I

    CO

    0C

    .~H5)

    2 H S

    CH

    ~

    I C~

    HsP

    (CH

    2--C

    HC

    00C

    aH02

    IF s

    CH

    a I

    C,H

    6P (C

    H._--C

    HCO

    OCaH

    T-I)~

    S

    CHa

    C,IIs

    P (C

    H2--~

    HCO

    OC4

    H.),

    II S

    C, H

    sP

    CH

    a !

    (CH

    ,--C

    HC

    O 0C

    4F[~

    -i)2

    C,H

    ~P (

    CH~

    CH,C

    OO

    CHs)

    , *

    II S

    C.t

    IsP (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 (C

    II ~

    CH~

    --~

    --CH

    a)~

    ****

    II S

    N

    ~84 (0

    ,3)

    194-

    -195

    (1

    ,5)

    t95

    --i9

    6 (0

    ,5)

    188-

    -189

    (0

    ,5)

    20

    8--

    2ti

    (0,5

    )

    19

    1,5

    --1

    92

    (i

    )

    20

    0--

    20

    1 (t)

    M.p

    . 5

    2--

    54

    ~

    M.p

    . 1

    02

    --1

    03

    ,5

    ~

    19

    9--

    t99

    ,5

    (1) o

    M

    .p.

    41--4

    2

    227 (t

    )

    M.p

    . lt

    a ~

    ~

    20

    nD

    Fo

    un

    d, %

    Ca

    lcu.

    . %

    ~

    RD

    i,t7

    03

    1,1

    43

    8

    i,0

    99

    7

    1,0

    99

    7

    1,0

    78

    9

    t,0

    70

    2

    t,1

    75

    4

    t,5

    47

    8

    1,5.

    403

    1,5

    25

    8

    1,5

    24

    2

    1,5

    2~

    9

    1,5

    i75

    t,5

    49

    4

    C 5

    6,3

    5

    P 9

    ,49

    P 6

    ,83

    P 8

    ,43

    P 7

    ,76

    P 7

    ,89

    C 6

    2,0

    0

    P 8

    ,38

    H

    7,2

    8

    P 7

    ,16

    C 5

    3,5

    P 9

    ,87

    tI

    6,0

    6

    C 5

    6,2

    5

    P 1

    2,0

    2

    H

    7,5

    1

    P 1

    2,0

    6

    t2,0

    1

    12

    ,43

    I2

    ,58

    P 9

    ,46

    P 8.

    26

    C 56

    ,4i

    P 9

    ,33

    H

    6,7

    6

    P 8

    ,37

    P 7

    ,78

    P 7

    ,79

    C 6

    t,9

    9

    P 8

    ,27

    H

    7,2

    8

    P 7

    ,28

    C 5

    3,46

    P

    9,56

    H

    6,0

    2

    C 5

    5,8

    1

    P 1

    2,0

    1

    H

    7,3

    6

    P i

    2,1

    0

    S 1

    2,5

    0

    P

    9,4

    8

    P

    8,t

    5

    92

    ,93

    101,

    66

    tlt,

    28

    tt0

    ,9t

    t20

    ,54

    t20

    ,67

    92

    ,70

    Found

    AR

    D

    6,3

    3

    5,8

    3

    6,2

    t

    5,8

    5

    6,2

    3

    6,2

    0

    6,t

    i

    Yie

    ld,

    73

    ,3

    83

    ,5

    85

    ,2

    80

    ,7

    75

    ,3

    73

    ,4

    91

    96,7

    66~

    6

    66

    ,1

    " 6

    2,2

    %

  • 0

    TABLE

    3

    No

    . 3

    4

    5 6 7

    8 9 10

    tt

    Fo

    rmu

    la

    CH

    2 i

    C,H

    ,P (C

    H~

    CH

    CO

    OCH

    ~)~

    U

    O

    C

    H,

    C,H

    sP (

    CH

    2--C

    HC

    OO

    C2H

    I) ,

    II 0 C

    rl~

    C,It

    , P "(

    CH

    ,~IIC

    O

    OC

    ~H

    ,h

    CtI

    8 C

    .H,P

    (CH

    =~

    HC

    OO

    C,H

    .-ih

    CIt=

    C

    tHsP

    (CH

    z~H

    CO

    OC

    ,II,)

    ~

    C,H

    sP (C

    II2CII2

    CH~

    NH,h

    II O

    C,H

    mP (C

    H,C

    HzO

    COCH,h

    [I o

    C. H

    ~[P

    (CH

    ~C

    H, OC

    H,)

    , "

    0

    N

    C,H

    sP (C

    H~

    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~

    CO

    OH

    h ****

    II O

    B.p

    . in

    *c

    (p

    in r

    am

    )

    19

    t,5

    --t9

    2 (1,5

    )

    t96

    ,5--

    t98

    (t,5

    )

    t97

    --i9

    8 (1

    )

    2i0

    --2

    11

    (1,5

    )

    209--210

    (l)

    179~

    180

    (1)

    223--224

    (i)

    M.p

    . 8

    4--

    85

    ~

    20

    1--

    20

    3 (2)

    M.p

    . 7

    t--7

    i,5

    ~

    22

    0--

    22

    3

    M.p

    . 7

    7--

    78

    ~

    M.p

    . i9

    9--

    20

    2

    ~

    1,t

    66

    4

    t,i2

    76

    t,0

    86

    3

    t,0

    62

    7

    t,0

    68

    0

    1,1

    20

    8

    t,t6

    t7

    20

    nD

    i,5

    17

    8

    1,5

    07

    9

    i ,5

    00

    6

    t,4

    95

    6

    t,4

    98

    7

    t,5

    66

    0

    1,5

    17

    8

    B

    Fo

    un

    d

    C 5

    8,7

    0

    P 9

    ,43

    H

    7

    ,16

    C 6

    0,9

    5

    P 8

    ,42

    H

    7,6

    5

    C 6

    2,6

    P

    8,0

    0

    H

    8,t

    9

    P 7

    ,8i

    P 7

    ,35

    C6

    0,1

    2

    P t2

    ,60

    H

    8,8

    7

    P 9

    ,72

    P 8

    ,62

    C 5

    6,2

    6

    P I0

    ,33

    H

    6,6

    C

    60

    ,08

    P

    i2,5

    H

    8

    ,i0

    %

    Cal

    cu.

    C 5

    8,9

    0

    P 9

    ,45

    H

    7

    ,13

    C 6

    i,0

    5

    P 8

    ,68

    H

    7,6

    8

    C 6

    2,6

    i P

    8,0

    9

    H

    8,i

    4

    P 7

    ,56

    P 7

    ,56

    C6

    0,0

    0

    P 1

    2,9

    1

    H 8

    ,75

    P 9

    ,45

    P 8

    ,52

    G 56,3

    7

    P I0

    ,4

    H 6

    ,37

    c 59

    ;5

    P 1

    2,8

    H

    7,8

    5

    Fou

    nd

    MR

    D

    84,7

    9

    93

    ,76

    i03

    ,70

    i12

    ,75

    i12

    ,79

    69

    ,93

    85

    AR

    D

    5,6

    9

    5,4

    3

    6,i

    2

    5,9

    3

    5,9

    8

    5,7

    6

    6,i

    6

    Yiel

    d,

    %

    54

    ,2

    6i,

    9

    52

    ,8

    79

    ,7

    81

    ,8

    44

    ,9

    81

    ,0

    58

    ,7

    76

    ,2

    -21

    75

    * Re

    cry

    sta

    lliz

    ed

    fr

    om

    he

    pta

    ne

    . *

    * Re

    cry

    sta

    lliz

    ed

    fr

    om

    eth

    er.

    *

    * * T

    he

    pro

    du

    ct wa

    s fra

    cti

    on

    ate

    d, an

    d th

    e c

    ryst

    all

    ine

    pa

    rt w

    as s

    ep

    ara

    ted

    a

    nd

    wa

    she

    d wit

    h e

    the

    r.

    * *

    * * R

    ecr

    yst

    all

    ize

    d

    fro

    m is

    op

    rop

    yl a

    lco

    ho

    l.

  • 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 ITERATURE C ITED

    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 avai lab le in Engl ish translation. A complete l i s t of the cover- to-

    cover Engl ish translat ions appears at the back of this issue.

    271

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