Functionalized aluminum reagents

Abstract

The invention is directed to functionalized aluminum reagents of formula 1 ##STR00001##
where R is a linear or branched alkane group containing 1 to 8 carbon atoms, and R.sup.1 is phenylene, or a linear or branched alkane diyl group containing 2 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; Q is of formula 2 ##STR00002##
where R.sup.5, R.sup.6 and R.sup.7 are independently a linear or branched alkyl group containing 1 to 3 carbon atoms or a group of formula 3 ##STR00003##
where R.sup.3 and R.sup.4 are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R.sup.3 and R.sup.4 taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; or R.sup.5, R.sup.6 and R.sup.7 taken together with the silicon atom represent a structure of formula 4 ##STR00004##
where R.sup.8 is C1 to C4 linear or branched alkanediyl and Z is N or a group of formula 5 ##STR00005##
wherein R.sup.13 is C1 to C8 alkyl.

Claims

1. A functionalized aluminum reagent of formula 1 ##STR00019## wherein R is a linear or branched alkane group containing 1 to 8 carbon atoms, and R.sup.1 is phenylene, or a linear or branched alkane diyl group containing 2 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; Q is of formula 2 ##STR00020## wherein R.sup.6, R.sup.7 and R.sup.8 are independently a linear or branched alkyl group containing 1 to 3 carbon atoms or a group of formula 3 ##STR00021## where R.sup.3 and R.sup.4 are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms wherein at least one of R.sup.6, R.sup.7 and R.sup.8 is of formula 3, or R.sup.3 and R.sup.4 taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; or R.sup.6, R.sup.7 and R.sup.8 taken together with the silicon atom represent a structure of formula 4 ##STR00022## wherein R.sup.9 is C1 to C4 linear or branched alkanediyl and Z is N or a group of formula 5 ##STR00023## wherein R.sup.13 is C1 to C8 alkyl.

2. The functionalized aluminum reagent of claim 1, selected from the group consisting of ##STR00024##

3. A method of making the functionalized aluminum reagent of claim 1, comprising the step of reaction of an olefinic silane 6 with a dialkyl aluminum hydride 7 in the presence of a neodymium catalyst ##STR00025## wherein R.sup.5 is phenylene, or a linear or branched alkane diyl group containing 1 to 9 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms, and R and Q are as previously defined.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a 2 Dimensional Correlational Analysis: NOSY.

(2) FIG. 2 shows a 2 Dimensional Correlational Analysis: COSY.

DESCRIPTION

(3) There are disclosed functionalized aluminum reagents formula 1

(4) ##STR00011##
where R is a linear or branched alkane group containing 1 to 8 carbon atoms, and R.sup.1 is phenylene, or a linear or branched alkane diyl group containing 2 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; Q is of formula 2

(5) ##STR00012##
where R.sup.6, R.sup.7 and R.sup.8 are independently a linear or branched alkyl group containing 1 to 3 carbon atoms or a group of formula 3

(6) ##STR00013##
where R3 and R4 are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R3 and R4 taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; or R.sup.6, R.sup.7 and R.sup.8 taken together with the silicon atom represent a structure of formula 4

(7) ##STR00014##
where R.sup.9 is C1 to C4 linear or branched alkanediyl and Z is N or a group of formula 5

(8) ##STR00015##
wherein R.sup.13 is C1 to C8 alkyl.

(9) There is further disclosed a method of making functionalized aluminum reagents.

(10) Functionalized aluminum reagents of formula 1 may be produced by reaction of an olefinic silane 6 with a dialkyl aluminum hydride 7 in the presence of a neodymium catalyst

(11) ##STR00016##
where R.sup.5 is phenylene, or a linear or branched alkane diyl group containing 1 to 9 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms, and R and Q are as previously defined.

(12) The reaction of the compounds of formulas 6 and 7 may be done neat at a temper-ature ranging from 25 to 90 C. for 12 to 72 hours. Optionally, the reaction may proceed in a hy-drocarbon solvent in the presence of a neodymium (III) catalyst.

(13) In one embodiment, the compound of formula 7 is diisobutyl aluminum hydride (DIBAL-H).

(14) In various embodiments, the functionalized aluminum reagent of formula 1 may be one of the following compounds A, B or C (Et=ethyl, Me=methyl):

(15) ##STR00017##
The functionalized aluminum reagents are useful for example as activators for lanthanide-based catalysts in polymerization of conjugated dienes.

(16) The invention is further illustrated by the following non-limiting examples.

Example 1

(17) Preformed Neodymium Catalyst

(18) The following reaction was performed in a nitrogen-filled glove box. To a 20 mL oven dried vial was added butadiene premix (6.0 mL, 15% w/w, 11.1 mmol, 40 equiv) and triiso-butylaluminium (6.4 mL, 25% w/w, 5.58 mmol, 20 equiv). Neodymium(III) versatate (560 L, 0.50 M, 0.279 mmol, 1.0 equiv) was then added, the vial was sealed with a teflon cap, and shaken for 60 minutes. Diethylaluminum chloride (700 L, 25% w/w, 0.697 mmol, 2.5 equiv) was then added and the catalyst was shaken overnight to produce a preformed neodymium catalyst.

(19) Synthesis of Compound A

(20) The following reaction was performed in a nitrogen-filled glove box. To a screw-cap NMR tube was added C.sub.6D.sub.6 (200 L), bis(diethylamino)methylvinyl silane (89 L, 0.25 mmol, 1.0 equiv), diisobutylaluminum hydride (275 L, 1.0 M in toluene, 0.275 mmol, 1.1 equiv), and the preformed neodymium catalyst (242 L, 0.0207 M, 0.0050 mmol, 2 mol %). The tube was sealed with a Teflon cap, removed from the glove box, and heated to 80 C. for 48 h. Analysis of the reaction mixture showed 81% conversion of the starting reagent.

(21) The reaction product was analyzed by 1D and 2D NMR with results given in Table 1 and FIGS. 1 and 2. Values are given as chemical shift (6) referenced to residual solvent.

(22) .sup.1H NMR: 7.15 ppm for C.sub.6D.sub.6.

(23) TABLE-US-00001 TABLE 1 Atom Predicted .sup.1H* Predicted .sup.13C* Observed .sup.1H Observed .sup.13C 3,4,8,10 2.8-3.0 39.9 2.5-3.0 38-42 5,6,9,11 1.1-1.2 17.0 0.75-1.0 18.4 12 0.12 4.7 0.0-0.2 4.5 13,14 0.5-0.6 26.4 0.2-0.4 12-14 16,20 0.31-0.37 19.3 0.1-0.26 22 17,21 1.85-1.95 25.0 2.0-1.75 25-28 18,19,22,23 0.9-1.0 26.4 1.0-1.2 27