Cycloaliphatic compounds

Details Cycloaliphatic compounds Cycloaliphatic compounds

1999-03-22

2001-06-05

Barts, Samuel (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Isocyanate esters

C560S336000, C564S462000, C564S461000, C568S329000, C568S721000, C568S315000

Reexamination Certificate

active

06242641

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to new cycloaliphatic compounds containing either isocyanate groups or isocyanate-reactive groups and to a process for their preparation.
SUMMARY OF THE INVENTION
The present invention relates to compounds corresponding to formula I
wherein
R
1
, R
2
, R
3
and R
4
are the same or different and represent hydrogen, C
1
, to C
6
-alkyl, C
5
to C
6
-cycloalkyl, phenyl and halogen,
m and n are the same or different and represent the 2, 3, 4 or 5,
X, A and B represent carbon and
Y
1
, Y
2
, Z
1
and Z
2
are the same or different and represent hydrogen, hydroxyl (OH), amino (NH
2
), isocyanato (NCO) or 4-hydroxyphenyl,
provided that
1) on at least one atom X one of the pairs, either R
1
and R
2
or R
3
and R
4
, are both alkyl and
2) if Y
1
and Y
2
each represent 4-hydroxyphenyl, then Z
1
represents hydroxyl (OH) and Z
2
represents hydrogen or Z
1
and Z
2
together denote an oxo group (═O) and
3) if one Y
1
, Y
2
, Z
1
or Z
2
is isocyanato (NCO) the remaining groups cannot represent hydroxyl (OH), amino (NH
2
) or 4-hydroxyphenyl and
4) if Y
1
or Y
2
denotes hydroxy (OH), Z
1
and Z
2
are not hydroxy (OH) or hydrogen (H) and
5) if Z
1
or Z
2
are hydroxy (OH), Y
1
and Y2 are not hydroxy (OH) or hydrogen (H) and
6) if Y
1
or Y
2
denotes amino (NH
2
), Z
1
and Z
2
are not hydrogen (H) and
7) if Z
1
or Z
2
are amino (NH
2
), Y
1
and Y
2
are not hydrogen (H).
The present invention also relates to a process for the preparation of these compounds.
DETAILED DESCRIPTION OF THE INVENTION
Preferably, on 1 to 2 X atoms, more preferably on only one X atom, either R
1
and R
2
or R
3
and R
4
both represent alkyl. The preferred alkyl radical is methyl. Preferably, the sum of n and m is four, and in particular m and n are each two. More preferably, m and n are each two and only the X atoms in the &agr;-position to a carbon atom A or B are substituted by two alkyl groups. Preferably, only one carbon atom, A or B, is substituted by two 4-hydroxyphenyl groups. Preferably, the compounds are difunctional, i.e., they contain two isocyanate-reactive groups or two isocyanate groups.
Preferred cycloalkane derivatives correspond to the formulas
The most preferred cycloalkane derivatives are 1,4-diamino-2,2,6-trimethylcyclohexane (formula Ia), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (formula Ib), 1-hydroxy-2,2,6-trimethyl-4-aminocyclohexane (formula Ic), 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethyl-4-hydroxycyclohexane (formula Id) and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethyl-4-oxocyclohexane (formula Ie).
The compounds of the formula I can be prepared in known manner, e.g., by the reductive amination of the diketones of formula II or III
wherein
R
1
, R
2
, R
3
, R
4
, X, A, B, m and n are as defined in formula I and
r, s and t are the same or different and represent the number 0, 1, 2, 3, 4 or 5, provided that the sum of r, s and t is n.
Using the preceding method, diamino compounds corresponding to formula I wherein Y
1
and Z
1
both represent amino (NH
2
) and Y
2
and Z
2
both represent hydrogen may be obtained.
Suitable cycloalkane derivatives also include aminoalcohols corresponding to formula (IV)
wherein
R
1
, R
2
, R
3
, R
4
, X, A, B, m and n are as defined in formula I,
Y
3
and Z
3
denote hydrogen and
either Y
4
and Z
4
represents amino (NH
2
), while the other represents hydroxyl (OH) may also be obtained from the starting materials of formula II or III.
Aminoalcohols corresponding to formula IV may also be obtained by reductive amination of the hydroxy-ketones of formula V or VI
wherein
R
1
, R
2
, R
3
, R
4
, X, A, B, m, n, r, s and t are as defined in formulas I, II and III and either
Y
3
and Y
4
together represent an oxo group (═O), Z
3
represents hydroxyl (OH) and Z
4
represents hydrogen, or
Z
3
and Z
4
together represent an oxo group (═O), Y
3
represents hydroxyl and Y
4
represents hydrogen.
The diketones of the formula II, III and the hydroxy-ketones of formula V and VI are known and described, e.g., in K. Mori, Tetrahedron vol. 30, 1065-1072 (1974), J. N. Marx, F. Sondheimer, Tetrahedron, Supp. 8, part I, 1-7 (1966), H. G. W. Leuenberger, W. Boguth, E. Widmer, R. Zell, Helvetica Chimica Acta, vol. 59, 1832-1849, (1976) and DE-A 2,4 57,158.
The reductive amination of ketones is also known and described, e.g., by W. Schneider, K. Lehmann in Methodicum Chimicum, volume 6, page 536 et seq. and R. Schröter, F. Möller in Houben-Weyl, volume XI/1, page 602 et seq. Further details for carrying out the reductive amination are found in DE 3,031,955, 3,011,656, 1,226,078 and 4,033,609. Suitable hydrogenation catalysts include Raney nickel, Raney cobalt, Pt or Pd. The reaction can be carried out at temperatures of 50 to 200° C. and pressures of 10 to 250 bar, optionally in the presence of a solvent and/or dehydrating agent.
Particularly preferred diketones of formula II and III and particularly preferred hydroxy-ketones of formula V and VI are compounds corresponding to the formula
The amino-alcohols of formula IV can also be obtained by the catalytic hydrogenation of imines corresponding to formula VII or VIII
wherein
R
1
, R
2
, R R
3
, R
4
, X, A, B, m, n, r, s and t are as defined in formulas I, II, III, V and VI
Z
3
represents hydrogen and Z
4
represents hydroxyl (OH) or Z
3
and Z
4
together represent an oxo group (═O) and
R represents hydrogen, benzyl, hydroxyl or a radical corresponding to formula IX or X
wherein
R
1
, R
2
, R
3
, R
4
, X, A, B, m, n, Z
3
, Z
4
, r, s and t are as defined in formula VII and VIII.
The diamino compounds corresponding to formula I wherein Y
1
and Z
1
both represent amino (NH
2
) and Y
2
and Z
2
both represent hydrogen may also be obtained by reductive amination of the imines of formula VII or VIII.
The imines of the general formula (VII) and (VIII) are accessible by methods known from the literature by reaction of the ketones of the general formulas (II), (III), (V) and (VI) with amine derivatives, such as e.g. ammonia, hydrazine, hydroxylamine and benzylamine (see, for example, Houben-Weyl, volume X/2, page 85 et seq. and volume 7/2b, page 1944 et seq.).
Preferred imines of the general formula (VII) and (VIII) are the compounds
The diisocyanato compounds of formula I wherein Y
1
and Z
1
both represent isocyanato (NCO) and Y
2
and Z
2
both represent hydrogen can be prepared by the phosgenation of the corresponding diamino compounds of formula I wherein Y
1
and Z
1
both represent amino (NH
2
) and Y
2
and Z
2
both represent hydrogen by known methods as described, e.g., in Houben-Weyl, volume VIII, page 119 et seq.
The dihydroxydiphenylcycloalkanes corresponding to formula I wherein
Y
1
and Y
2
both represent 4-hydroxyphenyl and either
Z
1
Z
2
represents hydrogen and Z
2
represents hydroxyl (OH) or
Z
1
and Z
2
together represent oxo grouping (═O) can be prepared in a known manner by the condensation of phenol with ketones corresponding to formulas II and V, wherein s and t are zero, in the presence of acid catalysts and optionally by addition of sulfur-containing co-catalysts. This condensation reaction is described, e.g., in Schnell, Chemistry and Physics of Polycarbonates, Inter-science Publishers, New York 1964 and in EP-A 359,953 and U.S. Pat. No. 5,210,328.
The compounds of the formula I are valuable intermediate products for the preparation and modification of polymers, such as polycarbonates, polyamides, polyureas and polyurethanes as described, e.g., in Houben-Weyl, volume E20, part 2.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.


REFERENCES:
patent: 5786438 (1998-07-01), Scholl et al.
patent: 2225229 (1998-06-01), None
patent: 19614269 (1997-10-01), None
patent: 19650042 (1998-06-01), None
Xiangdong He, et al, Journal of Applied Polymer Science, vol. 54, No. 2 Oct. 10, 1994, pp. 207-218.
Tanaka et al, Tetrahedron: Asymmetry, vol. 6, No. 6, Jun. 1, 1995, pp. 1273-1278.
Keana e

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