Method for producing 1-indanoles and 1-indanamines

Abstract

A description is given of a process for preparing 1-indanols and 1-indanamines by palladium-catalyzed arylation and of the use thereof as intermediates for the synthesis of fine chemicals and of active agrochemical ingredients.

Claims

1. A process for preparing a 1-indanol and/or a 1-indanamine of formula (I) which comprises reacting a 1-(2-halophenyl)alkan-1-ol or 1-(2-halophenyl)alkan-1-amine (II) at elevated temperature under palladium catalysis in the presence of one or more phosphine ligands, a base, and a solvent, ##STR00017## and in which the radicals, symbols, and indices are defined as follows: Y is NR.sup.1R.sup.2 or OR.sup.3, R.sup.1 is hydrogen or COR.sup.4, R.sup.2 is COR.sup.4, or R.sup.1 and R.sup.2 together form the group COCH.sub.2CH.sub.2CO or CO-phenylene-CO, R.sup.3 is Si(R.sup.5).sub.3 or 2,2-dimethylpropanoyl, R.sup.4 is (C.sub.1-C.sub.6)-alkyl or phenyl, R.sup.5 is (C.sub.1-C.sub.6)-alkyl or phenyl, Hal is chlorine, bromine or iodine, R is fluorine, (C.sub.1-C.sub.3)-alkyl or (C.sub.1-C.sub.3)-alkoxy, X.sup.1 is hydrogen or (C.sub.1-C.sub.6)-alkyl, X.sup.2 is hydrogen or (C.sub.1-C.sub.6)-alkyl, X.sup.3 is hydrogen or (C.sub.1-C.sub.6)-alkyl, X.sup.4 is hydrogen or (C.sub.1-C.sub.6)-alkyl, or X.sup.1 and X.sup.2, or X.sup.3 and X.sup.4, or X.sup.1 and X.sup.3 together with the carbon atom to which they are bonded form in each case a 3- to 7-membered saturated ring, or Y and X.sup.1 together with the carbon atoms to which they are bonded form a 5- to 7-membered saturated ring, m is 0, 1, 2 or 3.

2. The process as claimed in claim 1, in which the radicals, symbols, and indices have the following definitions: Y is NR.sup.1R.sup.2 or OR.sup.3, R.sup.1 is hydrogen or COR.sup.4, R.sup.2 is COR.sup.4, R.sup.3 is Si(R.sup.5).sub.3 or 2,2-dimethylpropanoyl, R.sup.4 is tert-butyl, R.sup.5 isisopropyl, Hal is bromine or iodine, R is fluorine, methyl or methoxy, X.sup.1 is hydrogen or methyl, X.sup.2 is hydrogen or methyl, X.sup.3 is hydrogen or methyl, X.sup.4 is hydrogen or methyl, or X.sup.1 and X.sup.2, or X.sup.3 and X.sup.4, or X.sup.1 and X.sup.3 together with the carbon atom to which they are bonded form in each case a 3- to 7-membered saturated ring, or Y and X.sup.1 together with the carbon atoms to which they are bonded form a 5- to 7-membered saturated ring, m is 0, 1, 2 or 3.

3. The process as claimed in claim 1, in which said palladium catalyst used is a compound from the group consisting of Pd(OAc).sub.2, tris(dibenzylideneacetone)dipalladium(0), PdCl.sub.2, and PdBr.sub.2.

4. The process as claimed in claim 3, in which Pd(OAc).sub.2 is used.

5. The process as claimed in claim 1, in which triphenylphosphine is used as ligand.

6. The process as claimed in claim 1, in which tetrakis(triphenylphosphinyl)palladium is used as combined palladium catalyst and ligand.

7. The process as claimed in claim 1, in which the palladium catalyst and the ligand or the combination thereof are/is used in each case in an amount of 0.1 to 10 mol %, based on the compound (II).

8. The process as claimed in claim 7, in which the palladium catalyst and the ligand or the combination thereof are/is used in each case in an amount of 1 to 5 mol %, based on the compound (II).

9. The process as claimed in claim 1, where said base used is a mixture of an alkali metal carbonate and an alkali metal pivalate.

10. The process as claimed in claim 1, where the base is used in a 1- to 5-molar proportion, based on the compound (II).

11. The process as claimed in claim 1, where said solvent used is from the group of the aromatics.

Description

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

(1) Suitable palladium catalysts are, for example, Pd(OAc)2, Pd2dba3 (tris(dibenzylideneacetone)dipalladium(0)), PdCl2, and PdBr2, with Pd(OAc)2 being preferred. The palladium catalyst is used customarily in an amount of 0.1 to 10 mol %, preferably 1 to 10 mol %, more preferably 1 to 5 mol %, based on the compound (II).

(2) Suitable phosphine ligands are, for example, trialkylphosphines, tricycloalkylphosphines such as tricyclohexylphosphine, triarylphosphines such as triphenylphosphine, tri-ortho-tolylphosphine, tri(4-dimethylaminophenyl)phosphines, and alkyldiarylphosphines such as butyldiphenylphosphine, with triphenylphosphine being particularly preferred. The phosphines may also be used in the form of salts, with HBF4, for example, The phosphine ligands are used customarily in an amount of 0.1 to 10 mol %, preferably 1 to 10 mol %, more preferably 1 to 5 mol %, based on the compound (II).

(3) Palladium catalysts and phosphine ligands can be used as separate compounds or usefully in the form of a preformed complex—for example, as tetrakis(triphenylphosphinyl)palladium, which is particularly preferred.

(4) Suitable bases are, for example, carbonates, hydrogencarbonates, phosphates, alkoxides, and carboxylates of alkali metals, such as Li.sub.2CO.sub.3, Na.sub.2CO.sub.3, K.sub.2CO.sub.3, NaHCO.sub.3, KHCO.sub.3, K.sub.3PO.sub.4, K.sub.2HPO.sub.4, NaOMe, NaOEt, NaOiPr, NaOtBu, KOMe, KOEt, KOiPr, KOtBu, NaOAc, KOAc, NaOPiv (sodium pivalate), KOPiv. NaOCOPh, and KOCOPh or mixtures of such bases. Mixtures of carbonates and carboxylates are preferred. The mixture of K.sub.2CO.sub.3 and KOPiv is particularly preferred. The base is used customarily in a 1- to 5-molar proportion, based on the compound (II).

(5) Suitable solvents are, for example, aromatics such as toluene, xylene, chlorobenzene, and anisole; ethers such as dibutyl ether, diphenyl ether, and polyglycol ethers; esters such as butyl acetate and isopropyl acetate; amides such as dimethylacetamide, dimethylformamide, and dibutylformamide, or mixtures thereof. Particularly preferred are aromatic solvents such as xylene.

(6) The preparation process of the invention is carried out customarily at elevated temperature of more than 100° C. up to the boiling point of the solvent in question. A range from 120 to 150° C. is preferred, Should the boiling point of the solvent in question be below this, it is useful to work under superatmospheric pressure.

(7) The process is carried out preferably for compounds of the formulae specified above in which the radicals, symbols, and indices are defined as follows: Y is NR.sup.1R.sup.2 or OR.sup.3, R.sup.1 is hydrogen or COR.sup.4, R.sup.2 is COR.sup.4, R.sup.3 is Si(R.sup.5).sub.3 or 2,2-dimethylpropanoyl, R.sup.4 is tert-butyl, R.sup.5 is isopropyl, Hal is bromine or iodine, R is fluorine, methyl or methoxy, X.sup.1 is hydrogen or methyl, X.sup.2 is hydrogen or methyl, X.sup.3 is hydrogen or methyl, X.sup.4 is hydrogen or methyl,
or X.sup.1 and X.sup.2, or X.sup.3 and X.sup.4, or X.sup.1 and X.sup.3 together with the carbon atom to which they are bonded form in each case a 3- to 7-membered saturated ring,
or Y and X.sup.1 together with the carbon atoms to which they are bonded form a 5- to 7-membered saturated ring, m is 0, 1, 2 or 3.

(8) In the formula (I) and all the formulae which follow, alkyl radicals having more than two carbon atoms may be straight-chain or branched. Alkyl radicals are, for example, methyl, ethyl, n- or isopropyl, n-, iso-, tert- or 2-butyl, pentyls, and hexyls, such as n-hexyl, isohexyl, and 1,3-dimethylbutyl.

(9) The examples which follow illustrate the invention.

(10) The abbreviations used here are:

(11) TABLE-US-00001 Ac acetate Cy cyclohexyl Cyp cyclopentyl Me methyl Ph phenyl Piv pivalate TiPs triisopropylsilyl
General instructions:

(12) Under inert gas, the palladium catalyst (0.015 mmol, 5 mol %), optionally the phosphine ligand (0.03 mmol, 10 mol %), and the base, e.g., potassium pivalate (0.030 mmol, 10 mol %) and K.sub.2CO.sub.3 (0.3 mmol, 1.0 eq) are introduced and the solvent (3 ml of xylene) and a compound of the formula (II) (0.3 mmol, 1.0 eq) are added. The mixture is then stirred at room temperature for 10 minutes and subsequently heated to 140° C. and stirred at this temperature for 16 hours. After the reaction mixture has cooled to room temperature it is filtered, the solvent is stripped off, and the residue is purified by chromatography.

EXAMPLE 1

Preparation of 2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)oxy)triisopropylsilane from [1-(2-bromophenyl)-2,2-dimethylpropoxy](triisopropyl)silane

(13) ##STR00004##

(14) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 89%.

(15) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.01 (s, 3H), 1.06-1.25 (m, 24H), 2.60 (d, J=15.2 Hz, 1H), 2.75 (d, J=15.2 Hz, 1H), 4.93 (s, 1H), 7.11-7.22 (m, 3H), 7.29-7.38 (m, 1H).

EXAMPLE 2

Preparation of ((2′,3′-dihydrospiro[cyclopropane-1,1′-inden]-3′-yl)oxy)triisopropylsilane from [1-(2-bromophenyl)-cyclopropylethoxy](triisopropyl)silane

(16) ##STR00005##

(17) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 69%.

(18) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 0.70-0.82 (m, 1H), 0.85-0.96 (m, 1H), 1.00-1.27 (m, 23H), 2.31 (d, J=7.2 Hz, 2H), 5.60 (t, J=7.2 Hz, 1H), 6.67-6.76 (m, 1H), 7.17-7.27 (m, 2H), 7.39-7.46 (m, 1H).

EXAMPLE 3

Preparation of ((5,6-dimethoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)oxy)triisopropylsilane from [1-(2-bromo-4,5-dimethoxyphenyl)-2,2-dimethylpropoxy](tri-tert-butypsilane

(19) ##STR00006##

(20) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 84%.

(21) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.02 (s, 3H), 1.06-1.25 (m, 24H), 2.53 (d, J=15.0 Hz, 1H), 2.69 (d, J=15.0 Hz, 1H), 3.85 (s, 6H), 4.86 (s, 1H), 6.69 (s, 1H), 6.89 (s, 1H).

EXAMPLE 4

Preparation of ((6-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)oxy)triisopropylsilane from [1-(2-bromo-5-methoxyphenyl)-2,2-dimethylpropoxy](tri-tert-butyl)silane

(22) ##STR00007##

(23) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 81%.

(24) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 0.98 (s, 3H), 1.05-1.28 (m, 24H), 2.54 (d, J=14.8 Hz, 1H), 2.65 (d, J=14.8 Hz, 1H), 3.79 (s, 3H), 4.90 (s, 1H), 6.73 (dd, J=2.5, 8.1 Hz, 1H), 6.89 (d, J=2.5 Hz, 1H), 7.04 (d, J=8.1 Hz, 1H).

EXAMPLE 5

Preparation of ((6-fluoro-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)oxy)triisopropylsilane from [1-(2-bromo-5-fluorophenyl)-2,2-dimethylpropoxy](tri-tert-butyl)silane

(25) ##STR00008##

(26) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 84%.

(27) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ1.00 (s, 3H), 1.06-1.26 (m, 24H), 2.55 (d, J=15.0 Hz, 1H), 2.68 (d, J=15.0 Hz, 1H), 4.90 (s, 1H), 6.87 (ddd, J=2.5, 81, 9.2 Hz, 1H), 7.00 (dd, J=2.5, 8.7 Hz, 1H), 7.07 (dd, J=5.2, 8.1 Hz, 1H).

EXAMPLE 6

Preparation of 2,2-dimethyl-2,3-dihydro-1H-inden-1-yl 2,2-dimethylpropanoate from 1-(2-bromophenyl)-2,2-dimethylpropyl 2,2-dimethylpropanoate

(28) ##STR00009##

(29) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 95%.

(30) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.09 (s, 3H), 1.16 (s, 3H), 1.21 (s, 9H), 2.69 (d, J=15.3 Hz, 1H), 2.87 (d, J=15.3 Hz, 1H), 5.81 (s, 1H), 7.09-7.29 (m, 4H).

EXAMPLE 7

Preparation of 6-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl 2,2-dimethylpropanoate from 1-(2-bromo-5-methoxyphenyl)-2,2-dimethylpropyl2,2-dimethylpropanoate

(31) ##STR00010##

(32) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 88%.

(33) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.09 (s, 3H), 1.16 (s, 3H), 1.22 (s, 9H), 2.63 (d, J=15.3 Hz, 1H), 2.80 (d, J=15.3 Hz, 1H), 3.77 (s, 3H), 5.79 (s, 1H), 6.77-6.84 (m, 2H), 7.05-7.12 (m, 1H).

EXAMPLE 8

Preparation of 6-fluoro-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl 2,2-dimethylpropanoate from 1-(2-bromo-5-fluorophenyl)-2,2-dimethylpropyl 2,2-dimethylpropanoate

(34) ##STR00011##

(35) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 76%.

(36) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.08 (s, 3H), 1.16 (s, 3H), 1.22 (s, 9H), 2.65 (d, J=15.4 Hz, 1H), 2.81 (d, J=15.4 Hz, 1H), 5.76 (s, 1H), 6.87-6.99 (m, 2H), 7.08-7.15 (m, 1H).

EXAMPLE 9

Preparation of (3aR*,8bS*)-3a-methyl-3,3a,4,8b-tetrahydro-2H-indeno[1,2-b]furan-2-one from 5-(2-bromophenyl)-4,4-dimethyldihydrofuran-2(3H)-one

(37) ##STR00012##

(38) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 88%.

(39) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.34 (s, 3H), 2.45 (d, J=17.8 Hz, 1H), 2.51 (d, J=17.8 Hz, 1H), 2.87 (d, J=16.4 Hz, 1H), 3.00 (d, J=16.4 Hz, 1H), 5.32 (s, 1H), 7.13-7.29 (m, 3H), 7.36 (d, J=7.2 Hz, 1H).

EXAMPLE 10

Preparation of 2-(2-methyl-2,3-dihydro-1H-inden-1-yl)isoindoline-1,3-dione from 2-[1-(2-bromophenyl)-2-methylpropyl]-1H-isoindole-1,3(2H)-dione

(40) ##STR00013##

(41) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 54% of the trans isomer.

(42) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.27 (d, J=6.8 Hz, 3H), 2.65 (dd, J=8.6, 15.6 Hz, 1H), 3.00-3.18 (m, 1H), 3.37 (dd, J=8.2, 15.6 Hz, 1H), 5.43 (d, J=8.2 Hz, 1H), 7.01 (d, J=7.6 Hz, 1H), 7.11-7.19 (m, 1H), 7.20-7.30 (m, 2H), 7.70-7.79 (m, 2H), 7.82-7.91 (m, 2H).

EXAMPLE 11

Preparation of 2-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)isoindoline-1,3-dione from 2-[1-(2-bromophenyl)-2,2-dimethylpropyl]-1H-isoindole-1,3(2H)-dione

(43) ##STR00014##

(44) The reaction took place in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4, and gave a yield of 86%.

(45) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 0.64 (s, 3H), 0.83 (s, 3H), 2.34 (d, J=15.6 Hz, 1H), 2.87 (d, J=15.6 Hz, 1H), 4.9 (s, 1H), 6.66-6.77 (m, 2H), 6.80-6.89 (m, 2H), 7.16-7.33 (m, 3H), 7.42-7.49 (m, 1H).

EXAMPLE 12

Preparation of (1R,2S)-2,6-dimethylindan-1-amine from 2-[1-(2-bromo-5-methylphenyl)-2-methylpropyl]-1H-isoindole-1,3(2H)-dione via 2-[(1R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]-1H-isoindole-1,3(2H)-dione

(46) ##STR00015##

(47) The reaction took place initially in line with the general instructions, with 5 mol % of Pd(PPh.sub.3).sub.4,

(48) and gave a yield of 55% of the primary product.

(49) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.24 (d, J=7.0 Hz, 3H), 2.25 (s, 3H), 2.58 (dd, J=8.0, 15.7 Hz, 1H), 2.97-3.15 (m, 1H), 3.32 (dd, J=8.2, 15.7 Hz, 1H), 5.37 (d, J=8.2 Hz, 1H), 6.80 (s, 1H), 7.03 (d, J=7.5 Hz, 1H), 7.14 (d, J=7.5 Hz, 1H), 7.70-7.78 (m, 2H), 7.80-7.90 (m, 2H).

(50) Then a solution of 0.17 mmol of 2-(2,6-dimethyl-2,3-dihydro-1H-inden-1-yl)isoindoline-1,3-dione in 1 ml of methanol and 1 ml of THF was admixed at 0° C. with 1.7 mmol of hydrazine hydrate. The mixture was then stirred at room temperature for 12 hours. The mixture was filtered and concentrated, The residue was partitioned between DCM and water, and the organic phase was isolated and washed with saturated NaHCO.sub.3. After drying over MgSO.sub.4 and concentration, the product was obtained as a solid with a yield of 98%.

(51) .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.25 (d, J=6.7 Hz, 3H), 1.68 (s, 2H), 1.90-2.08 (m, 1H), 2.35 (s, 3H), 2.44 (dd, J=9.5, 15.3 Hz, 1H), 2.99 (dd, J=7.7, 15.3 Hz, 1H), 3.76 (d, J=8.3 Hz, 1H) 7.01 (d, J=7.5 Hz, 1H), 7.08 (d, J=7.5 Hz, 1H), 7.13 (s, 1H).

EXAMPLE 13

Preparation of triisopropyl((2-methyl-2,3-dihydro-1H-inden-1-yl)oxy)silane from [1-(2-bromophenyl)-2-methylpropoxy](triisopropyl)silane

(52) ##STR00016##

(53) This reaction was executed with different palladium catalysts, phosphine ligands, and quantities of bases. The results of these experiments, achieved under various conditions, are set out in table form:

(54) TABLE-US-00002 Yield No. Pd cat. Phosphine K.sub.2CO.sub.3 KOPiv of theory 13a 5 mol % Pd(PPh.sub.3).sub.4 100 mol % 10 mol % 55% cis, 8% trans 13b 5 mol % Pd(OAc).sub.2 10 mol % PCy.sub.3 110 mol % 10 mol % 47% cis, 5% trans 13c 5 mol % Pd(OAc).sub.2 10 mol % PCyp.sub.3 110 mol % 10 mol % 41% cis, 5% trans 13d 5 mol % Pd(OAc).sub.2 10 mol % PPh.sub.3 100 mol % 10 mol % 57% cis, 6% trans 13e 5 mol % Pd(OAc).sub.2 10 mol % P(4- 100 mol % 10 mol % 48% cis, 9% trans Me.sub.2N—Ph).sub.3

(55) cis isomer: .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 0.99 (d, J=6.9 Hz, 3H), 1.08-1.25 (m, 21H), 2.56-2.68 (m, 2H), 2.92 (dd, J=7.1, 15.7 Hz, 1H), 5.29 (d, J=5.8 Hz, 1H), 7.17-7.25 (m, 3H), 7.35-7.43 (m, 1H).

(56) trans isomer: .sup.1H NMR (300 MHz, CDCl.sub.3, 293 K) δ 1.05-1.31 (m, 24H), 2.34-2.57 (m, 2H), 3.10-3.33 (m, 1H), 4.98 (d, J=5.0 Hz, 1H), 7.19-7.28 (m, 3H), 7.37-7.46 (m, 1H).