Processes for preparing tertiary aminoalkylorganometallic...

Details Processes for preparing tertiary aminoalkylorganometallic... Processes for preparing tertiary aminoalkylorganometallic...

2001-03-27

2002-11-19

Higel, Floyd D. (Department: 1626)

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

Organic compounds

Unsubstituted hydrocarbyl chain between the ring and the -c-...

C540S465000, C540S484000, C540S451000, C540S612000, C564S463000

Reexamination Certificate

active

06482944

ABSTRACT:

FIELD OF THE INVENTION
This invention is directed to processes for preparing haloamines and aminoalkylorganometallic compounds.
BACKGROUND OF THE INVENTION
Haloamines of the general formula R
1
R
2
N—(CH
2
)
n
—X (wherein X is halide) can be used for a variety of organic synthesis applications, such as precursors for functionalized amine initiators (U.S. Pat. No. 5,496,940) or as electrophiles for functionalization of polymers (Ueda, Hirao, and Nakahama,
Macromolecules,
23, 939-945 (1990)).
Some common literature synthetic methods for the preparation of haloamines involve the chlorination of an omega-amino alcohol with thionylchloride (Leonard and Durand,
J. Org. Chem.,
33, 1330 (1968), as represented below by Equation 1:
R
1
R
2
N—(CH
2
)
n
—OH+SOCl
2
→R
1
R
2
N—(CH
2
)
n
—Cl  Equation 1
Haloamines can also be prepared by the reaction of an omega-haloalcohol with an amine, as reported in Czech Patent CS 248547 B1 880701, represented below by Equation 2:
R
1
R
2
N—H+Cl—(CH
2
)
n
—OH→R
1
R
2
N—(CH
2
)
n
—Cl  Equation 2
These methods, however, can require very expensive raw materials and are typically inconvenient, due to the lack of availability of these raw materials, the omega-amino- and halo-alcohols.
U.S. Pat. No. 5,496,940 reports another method for preparing haloamines by the reaction of a lithium amide with the alkylhalide to form the haloamine, represented by Equation 3 below.
R
1
R
2
N—Li+Br—(CH
2
)
n
—Cl→R
1
R
2
N—(CH
2
)
n
—Cl+LiBr  Equation 3
This method, however, is also expensive. Further, there can be safety concerns associated with this method due to the employment of lithium-based reagents.
Haloamines such as those prepared as described above are useful for a variety of organic synthesis applications. For example, U.S. Pat. No. 5,496,940 reports a process for the preparation of aminoalkyllithium compounds by reacting a haloamine with two or more equivalents of an alkyllithium reagent, such as tert-butyllithium, in a solvent preferably at a temperature less than 38° C. An exemplary reaction is set forth below by Equation 4:
Monofunctional anionic initiators possessing amine functionalities are useful in preparing amino-terminated styrene-butadiene rubbers (SBRs). See European Patent Application 593049A1 and U.S. Pat. No. 5,496,940. These elastomers have been shown to possess increased rebound, decreased rolling resistance, and lower heat build-up (reduced hysteresis). They are useful in forming improved, energy efficient tires, power belts, and mechanical goods.
SUMMARY OF THE INVENTION
The present invention provides processes for preparing haloamines, which can avoid the economic and safety issues associated with prior procedures. In this aspect of the invention, haloamines are prepared by reacting an amine directly with an &agr;, &ohgr;-dihaloalkane or an &agr;, &ohgr;-dihaloalkene, optionally in the presence of an inorganic or organic acid acceptor, and optionally in a solvent. These haloamines can be prepared from inexpensive, readily available raw materials, namely, &agr;, &ohgr;-dihaloalkanes and &agr;, &ohgr;-dihaloalkenes and the corresponding amine.
The present invention also provides processes for the synthesis of aminoalkylorganometallic compounds. In this aspect of the invention, alkali metal, such as lithium, is reacted with a suitable haloamine, exclusively, in a hydrocarbon solvent to produce alkylalkali metal compounds containing tertiary amines. Because alkali metal, and not alkylorganometallic compounds, is used in the metallation of the haloamine, the processes of the invention can offer cost savings and safety improvements. In addition, unexpectedly, consistently higher yields can be obtained when the halogen-metal exchange reaction is conducted at elevated temperatures (>45° C.). Less unreacted starting material can also be present when the halogen-metal exchange is conducted at elevated temperatures. Still further, the Wurtz coupling by-product, for example, as illustrated by Equation 5, can be minimized when the halogen-metal exchange is conducted at elevated temperatures.
In addition, initiation of the metal-halogen exchange can be very consistent at the elevated temperatures. This consistent initiation can increase the safety of this process, in contrast to the methods detailed in the prior art.
DETAILED DESCRIPTION OF THE INVENTION
In one aspect of the invention, haloamines of the formula R
1
R
2
N—R
3
X
2
(I) (singly and mixtures) can be prepared, wherein:
R
1
and R
2
are independently chiral or achiral and independently selected from the group consisting of hydrogen; saturated or unsaturated, linear or branched, C1 to C16 alkyl; saturated or unsaturated C3-C16 cycloalkyl; saturated or unsaturated, linear or branched, silyl-, amino- or oxy-substituted C1-C16 alkyl; saturated or unsaturated silyl-, amino- or oxy-substituted C3-C16 cycloalkyl; saturated or unsaturated, linear or branched, substituted C1-C16 alkyl containing saturated or unsaturated linear or branched C1 to C8 lower alkyl, C3-C16 cycloalkyl, C3-C10 aryl, or substituted aryl containing saturated or unsaturated linear or branched C1-C8 lower alkyl or C3-C8 cycloalkyl; saturated or unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated linear or branched C1-C8 lower alkyl, C3-C8 cycloalkyl, C3-C10 aryl, or substituted aryl containing saturated or unsaturated linear or branched C1-C8 lower alkyl or C3-C8 cycloalkyl; or R
1
and R
2
together may represent a C4-C16 alkylene R
4
which alkylene may be saturated or unsaturated, optionally substituted with silyl, amino, or oxygen, or optionally substituted with saturated or unsaturated linear or branched C1-C8 alkyl, C3-C8 cycloalkyl, C3-C10 aryl, or substituted aryl containing saturated or unsaturated linear or branched C1-C8 lower alkyl or C3-C8 cycloalkyl;
R
3
is selected from the group consisting of saturated or unsaturated, linear or branched, C3-C25 alkyl; saturated or unsaturated C3-C25 cycloalkyl; saturated or unsaturated, linear or branched, substituted C3-C25 alkyl containing saturated or unsaturated linear or branched C1-C8 alkyl, C3-C8 cycloalkyl, C3-C10 aryl, or substituted aryl containing saturated or unsaturated linear or branched C1-C8 alkyl or C3-C8 cycloalkyl; saturated or unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated linear or branched C1-C8 alkyl, C3-C8 cycloalkyl, C3-C10 aryl, or substituted aryl containing saturated or unsaturated linear or branched C1-C8 alkyl or C3-C8 cycloalkyl; and
X
2
is halogen, such as chlorine and bromine.
Haloamines of Formula I can be prepared as illustrated below:
R
1
R
2
N—H+X
1
R
3
X
2
→R
1
R
2
N—R
3
X
2
+HX
1
wherein R
1
, R
2
, R
3
and X
2
are the same as defined above, and X
1
is also halogen which may be the same or different as X
2
.
Exemplary &agr;, &ohgr;-dihaloalkanes and &agr;, &ohgr;-dihaloalkenes include, but are not limited to, 1-bromo-3-chloro-propane, 1-bromo-4-chloro-butane, 1-bromo-5-chloro-pentane, 1-bromo-6-chloro-hexane, 1-bromo-8-chloro-octane, 1,4-dichloro-2-butene, 1,3-dibromopropane, 1,3-dichloropropane, 1,4-dibromobutane, 1,4-dichlorobutane, 1-bromo-3-chloro-2-methylpropane, 1,3-dibromo-2-methylpropane, 1,3-dichloro-2-methylpropane, 1,3-dichloro-2,2-dimethylpropane, 1,3-dibromo-2,2-dimethylpropane, 1-bromo-3-chloro-2,2-methylpropane, and the like, and mixtures thereof.
Examples of suitable amines useful in this invention include, but are not limited to, t-butyl amine, hexamethyleneimine, 1-methyl-1,4-diazacycloheptane (1-methylhomopiperazine), piperidine, pyrrolidine, ethyl amine, dimethyl amine, morpholine, 1-methyl piperazine, and the like, and mixtures thereof.
An inorganic or organic acid acceptor may be optionally employed in the synthesis described above. Examples of suitable acid acceptors include, but are not limited to, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, trimethylamine, and the like, and mixtures thereof.
Solvents (hydrocarbon and polar solvents) may be optionally e

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