tricyclic polyamines

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  • United States Patent 0 1

    3,470,248 TRICYC'LIC POLYAMINES

    Thomas K. Brotherton, Charleston, Robert J. Knopf, St. Albans, and Paul S. Starcher and Charles A. No?singer, Charleston, W. Va., assignors to Union Carbide Cor poration, a corporation of New York No Drawing. Filed Oct. 19, 1965, Ser. No. 498,091

    Int. Cl. C07c 87/40, 87/00; C07d 21/00 U.S. Cl. 260-563 Claims

    ABSTRACT OF THE DISCLOSURE Tricyclic polyamines and polyisocyanates which in

    clude decahydro-l,4-methanonaphthalene - 2,5 - ylenedi_ alkylene diamines and diisocyanates, dodecahydro-l,4 methanobenzocyclooctane-2,7(or 8)-ylenedialkylene di amines and diisocyanates, tricyclo[4.2.l.02'5]non-3,7(or 8)-ylenedialkylene diamines and diisocyanates, and hexa hydro-4,7-methanoindan-1 (or 2), 5 (or 6)-ylenedialkyl ene diamines and diisocyanates are useful in the resin arts such as in the preparation of urethane polymers, poly amides and polyurethane polyurea elastomers.

    The invention relates to tricyclic compositions and to various polymeric derivatives thereof. In one aspect, the invention relates to tricyclic polyamines and to various polymeric derivatives thereof. In another aspect, the in vention relates to tricyclic polyisocyanates and to various polymeric derivatives thereof. The tricyclic compositions of the invention are poly

    amino- or polyisocyanato-substituted tricyclic compounds. Among the tricyclic compositions that are within the scope of the invention are those that are represented by Formula I:

    i (I)

    wherein X represents isocyanato (NCO) or amino (NHZ); wherein R represents a saturated organic group of up to 20 carbon atoms and which can be unsubstituted or which can be substituted with ether oxygen (-O-, oxycarbonyl

    thio (-S), sulfone (SOz-), aminoalkyl, or iso cyanatoalkyl; wherein Y represents methylene, ethylene, ethylidene, alkoxy-substituted derivatives thereof, or my; wherein R2 represents hydrogen, alkyl, alkoxy, amino alkyl, or isocyanatoalkyl; and wherein G represents a saturated hydrocarbon group that can be unsubstituted or that can be substituted with alkyl, alkoxy, oxy, amino alkyl, or isocyanatoalkyl, and which, together with the two carbon atoms to which >G.RX is bonded, forms a cycloaliphatic ring of from 4 to 8 carbon atoms in the ring. A- second class of tricyclic compositions that are within the invention are compounds that have three fused saturated hydrocarbon rings, the said rings individually having from 4 to 8 carbon atoms provided that at least one of said rings has 6 carbon atoms, and wherein said compounds each contain at least two isocyanato or at least two amino groups. One highly desirable class of tricyclic compositions

    that are within the scope of the invention are the poly

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    60

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    3,470,248 Patented Sept. 30, 1969 ICC

    2 amines and polyisocyanates that are represented by Formula II:

    (II) (R91

    XCH CH: G-GHzX

    wherein X, R, and G have the meanings described above with respect to Formula I. Among the various com pounds that are represented by Formula II are the fol lowing:

    Decahydro - 8 - methyl - 1,4 - methanonaphthalen-2,5

    ylenedimethylene diisocyanate and diamine which can be produced by the following sequence of reactions: (1) Cyclopentadiene plus acrylonitrile to form S-norbor

    nene-Z-carbonitrile

    (2) S-norbornene-Z-carbonitrile plus sorbaldehyde (2,4 hexadienal) to form 2(or 3)-cyano-l,2,3,4,4a,5,8,8a octahydro - 8 - methyl - 1,4 - methanonaphthalene

    S-carboxaldehyde (I)

    CH3

    1 NC CH:

    (I) CH0 (3) (I) plus ammonia and hydrogen to form decahydro

    8 - methyl - 1,4 - methanonaphthalen - 2(or 3),5

    ylenedimethylene diamine (II)

    on, on.

    I main, | NO OH: > HINCH: CH: Raney I

    / Nickel /

    (1) CH0 (r1) (JHINHI

    (4) (II) plus phosgene to form decahydro-8-methyl-l,4 methanonaphthalen - 2(or 3),5-ylenedimethylene diiso Icyanate (III)

    ' CH3

    I 0001: HgNC H3 TH: -D

    (II) CHINE! CH3

    OCN C H CH2

    i/ (III) HgNC 0

    Reaction (1), above, is a conventional Diels-Alder reaction between cyclopentadiene and a dienophile. Diels Alder reactions are well known in the art, for instance,

  • 3,47 0,248 3

    see Organic Reactions, volume IV, edited by Roger Adams et 211., John Wiley & Sons, Inc., New York, pages 60173, particularly, pages 89-92. Reaction (2), above, is also a conventional Diels-Alder reaction. Reaction (3) above, is a combined hydrogenation and reductive alkyla tion (or reductive amination). The hydrogenation satu rates the ethylenic double bond and converts the nitrile group. Both types of reactions are Well known in the tion converts the aldehyde group to an aminomethyl group. Both types of reaction are well known in the art. For instance, reductive alkylation (or amination) is discussed in Organic Reactions, volume IV, pages 175 et seq. Reaction (4), above, is a conventional phosgenation reaction to form an isocyanate from a primary amine. Phosgenation reactions are well known in the art, for in stance, such reactions are described in US. Patents Nos. 2,680,127; 3,128,310 and 3,155,699; French Patent No. 1,368,031 and in an article by Siefken, Annalen Der Chemie, 562, pages 75-136 (1949).

    Also illustrative of the compounds that are represented by Formula II are dodecahydro-1,4-methanobenzocyclo octane-2,7(or 8)-ylenedimethylene diamine or diisocya nate which can be produced by the following sequence of reactions:

    10

    15

    20

    4 (4) Phosgenation of (VI) to form the diisocyanate (VII)

    i O 0 Cl: HzN CH TH: C HzNHz _->

    (VI)

    OCNCH CH2 CH2NCO

    (VII)

    Reaction \(3), above, is a conventional oxo reaction between an ole?n, carbon monoxide, and hydrogen to form an aldehyde. The 0x0 reaction is well known in the art as is illustrated by the article appearing in Encyclo pedia of Chemical Technology, volume 9, pages 699 et seq. (Interscience Publishers, Inc., New York, N.Y.). Formula II is also exempli?ed by decahydro-1,4

    methano-1H-benzocyclohepten-2,6(7 or 8)-ylenedimethyl ene diamine (VIII) and diisocyanate (IX), prepared by a route analogous to that employed to produce (VI) and (VII), except that the starting reactants are cyclo pentadiene and 1,4-cycloheptadiene.1 The molecular struc tures of these compounds are:

    azncnz

  • 3,47 0,248 6

    These compounds can be produced from dicyclopenta- (4) Reaction of the product of step (3) with ammonia dieue by the following sequence of reactions: and hydrogen produces the diamine (XVII), which is

    then reacted with phosgene to form the diisocyanate (1) I 00 HI I (XVIII). The molecular structures of these compounds

    (In. -0]0 0H0 CH: CH0 5 are represented by the following formulas: /

    (XVI) l (2) Reductive amination of (XVI) yields the diamine HzNCH Q CHzNHg

    (XIV) followed by phosgenation to produce the diiso- 10 I cyanate (XV). The molecular structures of these com~ pounds are: (XVII)

    ENCHy-EIJH; CHaNHl 15 OCN OIL-{I?j GHgNCO (XIV) (XVIII)

    I 20 A still further group of compounds that are illustrative OCNCH CHI CH1NCO of Formula II are 9~rnethylbricyclo[6.2.l.O2-"]undec-4(or

    5),l0-ylenedimethylene diamine (XIX) and diisocyanate X (XX). These compounds can be produced from cyclo

    ( v) _ _ pentadiene, crotonaldehyde, and butadiene by a sequence A further gl'mlP of compounds that a'l'? lllustl'atlve of 25 of reactions analogous to those immediately above. The

    Formula II are tricyclo[6-2-1-0-"]-unde-4(0r 5),9(l' molecular structures of these compounds are represented 10)-ylenedimethylene diamine (XVII) and diisocyanate by the formulas:

    CH2: cuzuco

    a 3 (XX) (XIX) '

    (XVIII). These compounds can be produced from cyclo- Additional illustrative compounds that are represented pentadiene, acrylonitrile, and butadiene by the following 35 by Formula II include 5-methyltricyclo[6.2.l.02"']undec sequence of reactions: 4,9(or l0)-ylenedimethylene diamine and diisocyanate (1) CH, ' (can be prepared from cyclopentadiene, acrylonitrile, and

    II/H D1918. I ON isoprene by a route analogous to that employed for pro & m CH: 40 ducing compounds XVII and XVIII, above); S-butyl N I tricyclo[6.2.1.02-7]undec-4,9(or 10)-ylenedimcthylene di

    amine and diisocyanate (can be prepared from cyclo (Z) No I 0H I pentadiene, acrylonitrile, and 1,3-octadienea by a route

    CH, +1!!! %1.s; NC CH, I analogous to that employed for producing compounds I .53 Md" I / 45 XVII and XVIII, above); and many other diamines and

    IIH V diisocyauates. For instance, another highly useful triamine and triisocyanate that are represented by Formula II is

    (3) I H I decahydro-1,4 - methanonaphthalene - 2,3,6 - (or 7 )-tri NC CH. go___: No. CH, .030 methylene triamine and triisocyanate that can be pro

    OXO 5o duced from fumaronitrile, cyclopentadiene, and butadiene by the following sequence of reactions:

    (11s on _ Dials, Butadiene, "' c Alde 9 Diele II t

    p c Alder

    (at W

    cu cu

    oac (ELIE. __.__. oxo

    CN c

    m1; 112 cuzmz cazuco ,

    I__, am 2M8 -z>ocncu2 CHgNl-lg Cl-IgNCO

    75 *Nazarov et 8.1., on. 54, 245231 (1960).

  • 3,470,248 7

    Also useful are decahydro-1,4-methanonaphthalene-2,6(or 7)-dimethylene-2-ethylene diamine and diisocyanate. These compounds can be produced by employing ita cononitrile in lieu of fumaronitrile in the process described immediately above. The formulas for these compounds are:

    112N011: CHzOHzNHg O CNCH

    The polyamines and polyisocyanates that are represent ed :by Formula II represent a preferred aspect of the poly arnines and polyisocyanates that are within the scope of F

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