Synthesis and reactions of halogen-containing compounds of the furan series

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  • CHEMISTRY OF HETEROCYCLIC COMPOUNDS 5

    SYNTttES1S AND REACTIONS OF ttALOGEN-CONTAINING COMPOUNDS OF THE FURAN SERIES

    I. Synthesis of a-Subst i tuted Tet rahydrofurans

    N. A. Ryabinin and I. P. Kolenko

    Khimiya Geterots ik l ichesk ikh Soedinenii , Vol. 4, No. 1, pp. 8 -10, 1968

    UDC 547. 722.3'727:542. 958.2

    A study of the interaction of a-chlorotetrahydrofuran with Grignard reagents and with secondary amines.

    The fundamental methods for obtaining tet rahydro- furan and its homologs are the hydrogenation of furan compounds [1-31 and the cyel izat ion of 1 ,4 -d io ls and of 1 ,4-ha lohydr ins [4]. Not long ago Bel' skii and Shuikin [5] descr ibed a method for the catalyt ic synthesis of tet rahydrofuran homologs, which cons isted of the hydrogenation of 1 - fury l -3 -a lkano ls in the vapor phase. In addition to these methods, a -subst i tuted tet rahy- drofurans may also be obtained by the interact ion of c~-ehlorotetrahydrofuran (I) with nueleophi l ie re - agents.

    The aim of the present invest igat ion was to study the interact ion of I with a lky l (ary l )magnesium hal ides and secondary amines. The Gr ignard reagents were prepared by the usual method, and pentaf luorophenyl- magnes ium chlor ide by the procedure descr ibed in the l i te ra ture [61. The react ion of I with Gr ignard reagents proceeded according to the usual pattern.

    ether Q']/N RMgX * ~ + MRCIX,

    C~ R

    X = Br; C1; R = propyl, butyl, amyl, hexyl, phenyl, o-tolyl, m-trifluoromethylpbenylene, pentafluoro- phenyl.

    The speed of the interact ion of I with alkylmagne~ slum hal ides depends on the nucleophi l ic i ty of the reagent , and on the temperature and concentrat ion of the react ing substances. Thus, I reacts very v io- lently with propy l - and buty lmagnesium bromides , and it is necessary to conduct the react ion with in- tensive s t i r r ing and good cooling. The react ion pro- ceeds more smoothly when diluted e therea l solut ions are employed. The interact ions of amyl - and hyxyl- magnes ium bromides , and of a ry lmagnes ium hal ides, with I proceed more smoothly and do not requ i re in- tensive cooling.

    The react ion mix tures were processed accord ing to the usual methods. The separat ion of pure alkyl- tet rahydrofurans was accompl ished by rect i f icat ion under normal or reduced pressure , depending on the boi l ing point of the substance. The table summar izes the data on the y ie lds of alkyl der ivat ives of te t rahy- drofuran and the i r e lementary analyses.

    F rom the interact ion of I with pyr idine, a quater - nary salt mel t ing at 219 ~ ~ C (deeomp.) is obtained. With morphol ine, I fo rms the corresponding amine with an 80% yield. With an excess of d iethylamine, I reacts to form c~-(N, N-d iethy l ) -aminotet rahydrofuran, but the yield is lower.

    It is known f rom the l i te rature [7,8] that o~,fl-di- ch lorotet rahydrofuran reacts with nucleophi l ic re - agents., such as a lcoholates , a lky l (a ry l )magnes ium- hal ides, and secondary amines, to form the cor re - sponding cr -subst i tuted- f i -ch lorotetrahydrofurans with more than 80% yield. In this case, the side react ion leading to the separat ion of a molecule of hydrogen chlor ide is pract ica l ly suppressed.

    As may be seen f rom the table, the yield of a -sub- st ituted te t rahydro furans , obtained by the interact ion of I with a lky l (ary l )magnes ium hal ides and secondary amines, is s igni f icant ly lower. This is espec ia l ly not iceable when the react ion is conducted with strong nucleophi l ic reagents . Evidently, this may be ex- plained by the presence of compet ing react ions , such as the separat ion of a molecule of hydrogen chlor ide, which leads to the format ion of 2 ,3-d ihydrofuran.

    EXPERIMENTAL

    a-Propylter.rahydrofutan (II). 106.5 g (1 mole) of I in 250 ml ab- solute ether was added at 0~ ~ C and under vigorous stirring in the course of 1-1 1/2 hr to a Grignard reagent prepared from 24 g (lg-at) of Mg and 122 g (1.1 mole) of ptopyl bromide in 300 ml of absolute ether. After adding the total quantity of I, the reaction temperature was gradually raised to room conditions, and then the reaction mix- ture was boiled for 1/2-1 hr, thus eliminating 5% of HCL Yield 66.7%.

    a-Butyletrahydrofuran was obtained by an analogous method. Compounds IV-IX were synthesized under somewhat different condi- tions. After adding the ethereal solution of I to the Grignard reagent, the temperature was raised to boiling, most of the ether distilled off, and the reaction mixture maintained for 1 3./2-2 hr at 800-90 ~ C. This was followed by treatment in the usual way.

    a-(N, N-Diethyl)aminotetrahydrofutan (X). 82 g (1.8 mole) of diethylamine in 160 ml of absolute ether was poured into a t~ee- necked reaction vessel provided with a dropping funnel, a stirrer, and a reflux condenser. Through the dropping funnel and under vigorous stirring and cooling by ice-water, 60 g of I in 150 ml of absolute ether was added drop by drop in the course of 1 hr. The reactionmass was allowed to stand overnight. The precipitated crystals were fil- tered-off, washed twice with ether, and the ethereal solution distilled off. Yield 40%.

    By an analogous procedure, a-(N-morpholyl) tetrahydrofuran (XI) is obtained with an 80% yield.

  • Cr~

    No.

    of

    Bp, *

    C (p

    ress

    ure,

    p

    rod

    uct

    Com

    poun

    d m

    m)

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    N 9

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    Hla

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    F F

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    X

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    o

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    nd

    Pro

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    -Su

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    ted

    T

    etr

    ah

    ydro

    fura

    ns

    131-

    -131

    .5

    (757

    158-

    -159

    (754

    )

    62--

    63 (1

    2)

    73.5

    --74

    (7)

    69.5

    --70

    (3)

    82--

    83 (3

    )

    96.5

    --97

    (12)

    90--

    91 (l

    l)

    0.86

    28

    0.86

    26

    0.86

    20

    0.86

    77

    1.03

    10

    1,03

    29

    1.23

    70

    1.45

    14

    2O

    n D

    .425

    0

    A315

    .436

    0

    .438

    5

    ,532

    0

    1,53

    62

    1.46

    76

    1.45

    08

    MRD

    Foun

    d Cal

    cu-

    tare

    d

    33.8

    0 34

    .32

    38.4

    4 38

    .97

    43.0

    8 43

    .62

    47

    .24

    47

    .27

    44.4

    8 44

    .77

    48,9

    1 ~4

    9,2

    2

    i 48

    .4~

    48.7

    1

    4~.1

    2 43.

    59 E

    mp

    iric

    al

    form

    ula

    C17H

    140

    C8H

    160

    C9H

    ,80

    CloH

    2oO

    CIo

    H20

    Cl1

    H1

    40

    Cn

    H.F

    sO

    CmH

    zFsO

    Foun

    d,

    9o

    7753

    .09~

    _

    7 iio

    76.1

    9 12

    .60 I

    --

    76.0

    a

    76.9

    2 12

    .80 [

    --

    76

    ,91

    80.9

    9 8

    .26

    / --

    ] 8

    1.08

    81,5

    8 8

    ,77

    ] --

    81

    ,42

    61.2

    6 4

    .98

    t --

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    6.3

    9 61

    .11

    / 50

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    2.83

    [ --

    /3

    9.8

    3 50

    .4

    67.0

    5 I 1

    .73

    9.6

    0

    67.1

    3

    60.5

    9,

    30 I

    8.79

    61

    .15

    61--

    62 (1

    2)

    97--

    98 (1

    2)

    0.93

    94 1

    .469

    8 42.

    46

    1.04

    28 1

    .475

    2 42.

    20 4

    2.76

    CaH

    I7N

    O

    ~2

    49

    CaH

    15N

    O2

    Cal

    cula

    ted

    , %

    " '

    "

    12.2

    8 /

    12.5

    0 [

    12.0

    7 l

    7,1j ~

    26.1

    9.79

    I --

    Yiel

    d,

    %

    66.7

    64.2

    58.0

    72.4

    69.9

    72.6

    60.6

    37.1

    40

    80.5

    >

    0 O

    r~

  • CHEMISTRY OF HETEROCYCLIC COMPOUNDS 7

    REFERENCES

    I. J. C loke and O. Ayers , J. Am. Chem. Soc., 56, 2144, 1934.

    2. A. A. Ponomarev , Synthesis and React ions of Furano id Compounds [in Russian], Izd-vo SGU, Sara- tov, 101, 1960.

    3. A. A. Ponomarev, Z. B. Til and V. A. Seda- vkina, ZhOKh, 33, 3951, 1963.

    4. A. Gipp, Ber . , 18, 3275, 1885. 5. I. F. Bel 'sk i i and N. I. Shuikin, DAN, 128,

    945, 1959.

    6. N. N. Vorzhtsov J r . , V. A. Barkhash, N. G. Ivanova, S. A. Anichkina, and O. I. Andreevskaya, DAN, 159, 125~ 1964.

    7. H~ Normant, C. r . , 226, 185, 1948. 8. L. Crombie and S. Harper, J . Chem. Soc.,

    1714, 1950.

    29 March 1966 Chemical Institute of the Ural Branch AS USSR, Sverdlovsk

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