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.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.

Claims

1. A functionalized aluminum reagent of formula 1 ##STR00021## 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 ##STR00022## wherein 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; wherein the functionalized aluminum reagent of formula 1 is selected from the group consisting of ##STR00023## ##STR00024## wherein TMS is a trimethylsilyl group.

2. The functionalized aluminum reagent of claim 1 selected from the group consisting of structures 1a and 1b.

3. The functionalized aluminum reagent of claim 1 selected from the group consisting of structures 1c and 1d.

4. The functionalized aluminum reagent of claim 1 having the structure 1e.

5. The functionalized aluminum reagent of claim 1 selected from the group consisting of structures 1f, 1g, 1h and 1i.

6. The functionalized aluminum reagent of claim 1 selected from the group consisting of structures 1j and 1k.

7. The functionalized aluminum reagent of claim 1 having the structure 11.

Description

DESCRIPTION

(1) There are disclosed functionalized aluminum reagents of formula 1

(2) ##STR00005##
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

(3) ##STR00006##
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.

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

(5) Functionalized aluminum reagents of formula 1 and 2 may be produced by reaction of a compound of formula 3 with a dialkyl aluminum hydride of formula 4

(6) ##STR00007##
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 is as previously defined.

(7) The reaction of the compounds of formulas 3 and 4 may be done neat at a temperature ranging from 25 to 75 C for 12 to 36 hours. Optionally, the reaction may proceed in a hydrocarbon solvent in the presence of a neodymium (III) catalyst.

(8) In one embodiment, the compound of formula 4 is diisobutyl aluminum hydride (DIBAL-H).

(9) In various embodiment, the functionalized aluminum reagent of formula 1 may be one of the following compounds 1a-1l.

(10) ##STR00008## ##STR00009##

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

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

Example 1

(3-Diphenylaminopropyl)diisobutyl Aluminum (1a)

(13) N,N-Diphenyl-N-allylamine (418 mg, 2 mmol), DIBAL-H (327 mg, 2.3 mmol), Nd(versatate).sub.3 (163 mg solution in hexanes, 100 mol, 5 mol %), and 92 mg C.sub.6D.sub.6 were combined in an 8 mL screw-cap vial and stirred for 14 h at 323 K. The resulting solution contains 1 mol Nd and ca 20 mol of (3-Diphenylaminopropyl)diisobutyl aluminum (1a) per 10 mg solution and was used without further purification.

(14) ##STR00010##

(15) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 7.06 (m, 4H, 2- and 6-H), 6.93 (m, 4H, 3- and 5-H), 6.83 (m, 2H, 4-H), 3.02 (t, .sup.3J.sub.HH=6.0 Hz, 2H, 7-H.sub.2), 2.03 (n, .sup.3J.sub.HH=6.6 Hz, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), (1.76 (m, 2H, 8-H.sub.2), 1.18 (d, .sup.3J.sub.HH=6.6 Hz, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.53 (m, 2H, 9-H.sub.2), 0.11 (d, .sup.3J.sub.HH=6.6 Hz, 4H, 2(CH.sub.3).sub.2CHCH.sub.2Al). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300 K): 149.84 (C.sub.q, C1), 129.04 (CH, C3 and C5), 126.56 (CH, C4), 124.80 (CH, C2 and C6), 60.51 (C7), 28.69 (2(CH.sub.3).sub.2CHCH.sub.2Al), 27.13 (2(CH.sub.3).sub.2CHCH.sub.2Al), 24.90 (2(CH.sub.3).sub.2CHCH.sub.2Al), 22.04 (C8), 3.75 (C9).

Example 2

(5-Diphenylaminopentyl)diisobutyl Aluminum (1b)

(16) N,N-Diphenyl-N-pent-4-enylamin (475 mg, 2 mmol), and DIBAL-H (291 mg, 2.05 mmol) were combined in a 8 mL screw-cap vial and stirred for 14 h at 323 K after which 1b had formed in ca 93% along with traces of isobutene.

(17) ##STR00011##

(18) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 7.11 (m, 4H, 3- and 5-H), 7.01 (m, 4H, 2- and 6-H), 6.83 (m, 2H, 4-H), 3.54 (t, .sup.3J.sub.HH=7.3 Hz, 2H, 7-H.sub.2), 1.95 (m, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), (1.63 (m, 2H, 8-H.sub.2), 1.49 (m, 2H, 10-H.sub.2), 1.31 (m, 2H, 9-H.sub.2), 1.03 (d, .sup.3J.sub.HH=7.2 Hz, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.3 (br, 6H, 11-H.sub.2 and 2(CH.sub.3).sub.2CHCH.sub.2Al). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300 K): 148.72 (C6), 129.51 (C3 and C5), 121.91 (C4), 121.42 (C2 and C6), 53.23 (C7), 33.13 (C9), 28.27 (2(CH.sub.3).sub.2CHCH.sub.2Al), 27.21 (C8), 26.43 (2(CH.sub.3).sub.2CHCH.sub.2Al), 25.56 (C10), 23.99 (br, 2(CH.sub.3).sub.2CHCH.sub.2Al), 11.52 (br, C11).

Example 3

(3-(9H-carbazol-9-yl)propyl)diisobutyl Aluminum (1c)

(19) N-Allylcarbazole (2073 mg, 10 mmol), and DIBAL-H (1500 mg, 10.5 mmol) were combined in a 8 mL screw-cap vial and stirred for 16 h at 323 K after which 1c had formed >95% along with traces of isobutene. 1c was alternatively prepared within 24 h at 298 K in the presence of 5 mol % Nd(versatate).sub.3.

(20) ##STR00012##

(21) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 7.68 (m, 2H, 2-H), 7.19 (m, 2H, 4-H), 7.09 (m, 4H, 3- and 5-H), 3.40 (t, .sup.3J.sub.HH=6.6 Hz, 2H, 7-H.sub.2), 1.80 (m, 2H, 8-H.sub.2), 1.71 (m, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.91 (d, .sup.3J.sub.HH=6.4 Hz, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.06 (m, 2H, 9-H.sub.2), 0.16 (m br, 4H, 2(CH.sub.3).sub.2CHCH.sub.2Al). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300 K): 145.30 (C1), 126.68 (C4), 126.43 (C6), 122.17 and 112.85 (C3 and C5), 120.71 (C2), 53.88 (C7), 28.24 (2(CH.sub.3).sub.2CHCH.sub.2Al), 26.24 (2(CH.sub.3).sub.2CHCH.sub.2Al), 25.92 (C8), 24.40 (2(CH.sub.3).sub.2CHCH.sub.2Al), 8.36 (C9).

Example 4

(5-(9H-carbazol-9-yl)pentyl)diisobutyl Aluminum (1d)

(22) N-Pent-4-enylcarbazole (1177 mg, 5 mmol), and DIBAL-H (780 mg, 5.48 mmol) were combined in a 8 mL screw-cap vial and stirred for 16 h at 323 K after which 1d had formed >95% along with traces of isobutene. 1d was alternatively prepared within 4 h at 343K, or within 24 h at 298K in presence of 5 mol % Nd(versatate).sub.3.

(23) ##STR00013##

(24) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 8.01 (m, 2H, 2-H), 7.37 (m, 2H, 4-H), 7.18 (m, 4H, 3- and 5-H), 3.81 (t, .sup.3J.sub.HH=6.8 Hz, 2H, 7-H.sub.2), 1.90 (m, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 1.56 (m, 2H, 8-H.sub.2), 1.22 (m, 2H, 10-H.sub.2), 1.14 (m, 2H, 9-H.sub.2) 1.02 (d, .sup.3J.sub.HH=6.4 Hz, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.21 (m, 4H, 4H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.35 (m br, 11-H.sub.2). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300 K): 140.93 (C1), 125.90 (C4), 123.48 (C6), 120.79 (C2), 119.14 and 109.06 (C3 and C5), 42.92 (C7), 33.23 (C9), 28.73 (C8), 28.26 (2(CH.sub.3).sub.2CHCH.sub.2Al), 26.30 (2(CH.sub.3).sub.2CHCH.sub.2Al), 25.37 (C10), 24.8 (v br, 2(CH.sub.3).sub.2CHCH.sub.2Al), 12.12 (C11).

Example 5

(3-(10H-phenothiazin-10-yl)propyl)diisobutyl Aluminum (1e)

(25) N-Allylphenothiazin (1197 mg, 5 mmol), and DIBAL-H (700 mg, 4.92 mmol), and C.sub.6D.sub.6 (603 mg) were combined in a 8 mL screw-cap vial and stirred for 16 h at 323 K after which 1d had formed >90%. The resulting solution contains 20 mol 1e per 10 mg solution.

(26) ##STR00014##

(27) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 7.07, 6.87, and 6.69 (m:m:m, 2:2:4H, 2-H to 5-H), 3.45 (t, .sup.3J.sub.HH=5.2 Hz, 7-H.sub.2), 2.00 (m, 2H, 8-H.sub.2), 1.80 (m, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 1.02 (br, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.24 (t, .sup.3J.sub.HH=6.8 Hz, 9-H.sub.2), 0.03 (br, 2(CH.sub.3).sub.2CHCH.sub.2Al). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300 K): 146.02 and 122.78 (C1 and C6), 128.92, 128.24, 124.77, and 118.41 (C2-C5), 53.80 (C7), 28.49 (2(CH.sub.3).sub.2CHCH.sub.2Al), 26.93 (2(CH.sub.3).sub.2CHCH.sub.2Al), 25.18 (2(CH.sub.3).sub.2CHCH.sub.2Al), 24.70 (C8), 8.93 (C9).

Example 6

(3-(1H-indol-1-yl)propyl)diisobutyl Aluminum (1f)

(28) N-Allylindol (1572 mg, 10 mmol), and DIBAL-H (1480 mg, 10.4 mmol) were combined in a 8 mL screw-cap vial and stirred for 16 h at 323 K after which 1f had formed >95%.

(29) ##STR00015##

(30) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 7.51, 7.14, and 7.05 (m each, 1:1:2H, 2-H to 5-H), 6.67 and 6.42 (br each, 1:1H, 7-H and 8-H), 3.43 (m br, 2H, 9-H.sub.2), 1.79 (m br, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 1.59 (m br, 10-H.sub.2), 0.98 (d, .sup.3J.sub.HH=6.4 Hz, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.09 (br, 6H, 11-H.sub.2 and 2(CH.sub.3).sub.2CHCH.sub.2Al). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300 K): 139.08 and 129.96 (C1 and C6), 126.48 and 105.28 (C7 and C8), 124.80, 122.45, 121.28, and 110.93 (C2-C5), 50.83 (C9), 28.30 (2(CH.sub.3).sub.2CHCH.sub.2Al), 26.38 (2(CH.sub.3).sub.2CHCH.sub.2Al), 26.13 (C10), 24.51 (2(CH.sub.3).sub.2CHCH.sub.2Al), 9.82 (C11).

Example 7

(5-(1H-indol-1-yl)pentyl)diisobutyl Aluminum (1g)

(31) N-Pent-4-enylindol (927 mg, 5 mmol), and DIBAL-H (720 mg, 5.06 mmol) were combined in a 8 mL screw-cap vial and stirred for 16 h at 323 K after which 1g had formed >95%.

(32) ##STR00016##

(33) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 7.69 and 7.17 (m each, 1:3H, 2-H to 5-H), 6.90 and 6.45 (br each, 1:1H, 7-H and 8-H), 3.61 (m, 2H, 9-H.sub.2), 1.92 (m, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 1.54 (m, 2H, 10-H.sub.2), 1.28 (m br, 2H, 12-H.sub.2), 1.14 (m br, 2H, 11-H.sub.2), 1.05 (d, .sup.3J.sub.HH=6.8 Hz, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.20 (m br, 4H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.06 (m br, 2H, 13-H.sub.2). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300 K): 137.10 and 129.66 (C1 and C6), 130.85 and 97.85 C7 and C8), 122.40, 121.74, 120.39, and 110.12 (C2-C5), 46.63 (C9), 33.02 (C11), 29.75 (C10), 28.37 (2(CH.sub.3).sub.2CHCH.sub.2Al), 26.48 (2(CH.sub.3).sub.2CHCH.sub.2Al), 25.54 (C12), 24.59 (2(CH.sub.3).sub.2CHCH.sub.2Al), 11.65 (C13).

Example 8

(3-(3-methyl-1H-indol-1-yl)propyl)diisobutyl Aluminum (1h)

(34) N-Allyl-3-methylylindol (856 mg, 5 mmol), and DIBAL-H (720 mg, 5.06 mmol) were combined in a 8 mL screw-cap vial and stirred for 16 h at 323 K after which 1g had formed >95%.

(35) ##STR00017##

(36) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 7.33, 7.09, and 7.05 (m each, 1:1:2H, 2H to 5-H), 6.37 (s, 1H, 8-H), 3.31 (t, .sup.3J.sub.HH=6.2 Hz, 9-H.sub.2), 2.06 (s, 3H, 12-H.sub.3), 1.79 (m br, 2H, 10-H.sub.2), 1.71 (m br, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.91 (d, .sup.3J.sub.HH=6.8 Hz, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.11 (m br, 2H, 11-H.sub.2), 0.20 (m br, 4H, 2(CH.sub.3).sub.2CHCH.sub.2Al). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300 K): 141.96 and 131.60 (C1 and C6), 124.6, 121.89, 120.43, and 112.47 (cC2-C5 and C8), 109.7 (C7), 52.44 (C9), 28.37 (2(CH.sub.3).sub.2CHCH.sub.2Al), 26.40 (2(CH.sub.3).sub.2CHCH.sub.2Al), 25.80 (C10), 23.73 (2(CH.sub.3).sub.2CHCH.sub.2Al), 9.98 (C12), 8.77 (C11).

Example 9

(3-(indolin-1-yl)propyl)diisobutyl Aluminum (1i)

(37) N-Allylindolin (796 mg, 4 mmol) and DIBAL-H (595 mg, 4.18 mmol) were combined in a 8 mL screw-cap vial and stirred for 16 h at 343 K after which 1i had formed >90%. Due to coordination of aluminum to the nitrogen atom, 7-11-CH.sub.2 exhibit diastereotopic protons, likewise the iBu groups become fully diastereotopic.

(38) ##STR00018##

(39) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 6.94 and 6.87 (m each, 1:2H, 3-, 4-, and 5-H), 6.78 (m, 1H, 2-H), 3.54 and 2.24 (m each, 1:1H, 8-H.sub.2), 3.06 and 2.24 (m each, 1:1H, 9-H.sub.2), 2.79 and 2.42 (m each, 1:1H, 7-H.sub.2), 1.98 and 1.61 (m each, 1:1H, 10-H.sub.2), 1.98 and 1.76 (2(CH.sub.3).sub.2CHCH.sub.2Al), 1.10, 1.06, 0.99, and 0.86 (d each, .sup.3J.sub.HH=6.4 Hz, 12H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.29 (m, 2H, 11-H.sub.2), 0.06 and 0.25 (m each, 2:2H, 2(CH.sub.3).sub.2CHCH.sub.2Al). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300K): 149.11 (C1), 133.52 (C6), 127.26, 125.71, and 125.24 (C3-C5), 117.06 (C2), 63.03 (C9), 57.97 (C8), 28.87, 28.84, 28.78, 28.74, and 28.41 (2(CH.sub.3).sub.2CHCH.sub.2Al and C7), 27.27 and 26.92 (2(CH.sub.3).sub.2CHCH.sub.2Al), 23.51 (C10), 23.41 and 23.06 (2(CH.sub.3).sub.2CHCH.sub.2Al), 4.58 (C11).

Example 11

(3-(phenyl(trimethylsilyl)amino)propyl)diisobutyl Aluminum (1k)

(40) N-Allyl-N-phenyl-N-trimethylsilyamine (1097 mg, 5 mmol), DIBAL-H (782 mg, 5.5 mmol), Nd(versatate).sub.3 (407 mg solution in hexanes, 250 mol), and 214 mg C.sub.6D.sub.6 were combined in a 8 mL screw-cap vial and stirred for 16 h at 343 K after which 1k had formed ca 95%. The solution contains 1 mol Nd and ca 20 mol 1k per 10 mg solution.

(41) ##STR00019##

(42) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 6.95 and 6.85 (m each, 4:1H, 2-H to 5-H), 2.98 (t, .sup.3J.sub.HH=6.4 Hz, 7-H.sub.2), 2.05 (m, 2H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 1.91 (m, 2H, 8-H.sub.2), 1.16 (d, .sup.3J.sub.HH=6.4 Hz, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.39 (m, 2H, 9-H.sub.2), 0.22 (m br, 4H, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.02 (s, 9H, TMS). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300K): 145.75 (C1), 128.37, 125.48, and 124.99 (C2-C5), 54.74 (C7), 28.75 (2(CH.sub.3).sub.2CHCH.sub.2Al), 27.21 (2(CH.sub.3).sub.2CHCH.sub.2Al), 26.00 (2(CH.sub.3).sub.2CHCH.sub.2Al), 23.13 (C8), 3.28 (C9), 0.18 (TMS).

Example 12

(3-(pyrrolidin-1-yl)propyl)diisobutyl Aluminum (1l)

(43) N-Allylpyrrolidin (556 mg, 5 mmol), DIBAL-H (740 mg, 5.2 mmol), Nd(versatate).sub.3 (163 mg solution in hexanes, 100 mol, 2 mol %) were combined in a 8 mL screw-cap vial and stirred for 20 h at 343 K after which 1j had formed in ca 95%. Due to coordination of aluminum to the nitrogen atom, 1- and 2-CH.sub.2 as well as (CH.sub.3).sub.2CHCH.sub.2Al exhibit diastereotopic protons.

(44) ##STR00020##

(45) .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 300 K): 2.85 and 1.84 (m each, 2:2H, 21-H.sub.2), 2.17 (t, .sup.3J.sub.HH=6.0 Hz, 3-H.sub.2), 1.95 (2(CH.sub.3).sub.2CHCH.sub.2Al), 1.60 (m, 2H, 4-H.sub.2), 1.48 and 1.34 (m each, 2:2H, 22-H.sub.2), 1.08 (d, 3J.sub.HH=7.6 Hz, 2(CH.sub.3).sub.2CHCH.sub.2Al), 0.133 (t, .sup.3J.sub.HH=7.6 Hz, 5-H.sub.2), 0.03 and 0.12 (dd each, .sup.2J.sub.HH=14.0 Hz, .sup.3J.sub.HH=7.6 Hz, 2(CH.sub.3).sub.2CHCH.sub.2Al). .sup.13C NMR (100 MHz, C.sub.6D.sub.6, 300K): 62.55 (C3), 54.98 (C1), 28.96 (2(CH.sub.3).sub.2CHCH.sub.2Al), 27.35 (2(CH.sub.3).sub.2CHCH.sub.2Al), 24.00 (C4), 23.00 (2(CH.sub.3).sub.2CHCH.sub.2Al), 22.86 (C2), 4.66 (C5).