Hydroformylation processes of making 2-(octahydro-1h-4,7-methanoinden-5-yl)acetaldehyde

Abstract

This disclosure relates to a process involving: contacting Compound (IV) with syngas in a reaction zone in the presence of a cobalt catalyst to form a product mixture comprising Compound (I), wherein the cobalt catalyst is (i) Co2(CO)8 or (ii) a mixture of Co2(CO)8 and a cobalt compound selected from the group of Co(acac)2, Co(acac)3, Co(OAc)2, Co(OH)2, mixtures of CoCl2 and an alkali metal carbonate, and combinations thereof. This disclosure also relates to a process involving: contacting Compound (IV) with syngas in a reaction zone in the presence of a heterogeneous or homogeneous rhodium catalyst to form a product mixture comprising Compound (I). This disclosure also relates to a compound of structural formula (III) in the form of any one of its stereoisomers or a mixture thereof. This disclosure also relates to a mixture of Compounds (I), (II) and (III).

Description

[0001] IFF-10187-WO-PCT

[0002] TITLE

[0003] Hydroformylation Processes of Making 2- (Octahydro- 1 H-4,7-methanoinden-5- yl)acetaldehyde

[0004] BACKGROUND

[0005] Reid of the Disclosure

[0006] The present disclosure relates to a hydroformylation process of making 2- (octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I, Aquaflora™ fragrance) by using a cobalt catalyst. The present disclosure also relates to a hydroformylation process of making 2-(octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde by using a heterogeneous or homogeneous rhodium catalyst. The present disclosure also relates to a new compound 5-methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde (Compound III). The present disclosure also relates to a mixture of Compound I, Compound II and Compound III, as well as fragrance compositions or consumer products comprising such mixture.

[0007] Description of Related Art

[0008] IFF (International flavors & Fragrances, Inc.) Aquaflora™ fragrance is a powerful watery, clean floralizer, even at low dosages. It offers violet undertones and can modernize orris notes. With outstanding bloom performance on skin and cloth, Aquafl ora™ frag rance boosts naturalcy and freshness. Therefore, there is an ongoing need to develop processes to make the Aquaflora™fragrance.

[0009] BRI EF SU M M A RY OF TH E D I SCLOSU RE

[0010] The present disclosure provides a hydroformylation process for making 2- (octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I). Tie process comprises: contacting Compound IV IFF-10187-WO-PCT wherein one of the symbols --- is a single bond and the other is a double bond, with carbon monoxide and hydrogen in a reaction zone in the presence of a cobalt catalyst to form a product mixture comprising Compound I, wherein the cobalt catalyst is (i) dicobalt octacarbonyl or (ii) a mixture of dicobalt octacarbonyl and a cobalt compound selected from the group of cobalt(ll) acetylacetonate, cobalt(lll) acetylacetonate, cobalt(ll) acetate, cobalt(ll) hydroxide, mixtures of cobalt(ll) chloride and an alkali metal carbonate, and combinations thereof.

[0011] The present disclosure also provides a hydroformylation process for making 2- (octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I). The process comprises: (a) contacting Compound IV with carbon monoxide and hydrogen in a reaction zone in the presence of a heterogeneous rhodium catalyst to form a product mixture comprising Compound I, wherein the heterogeneous rhodium catalyst comprises carbonyl(hydro)tris[tris(3-sulfophenyl)phosphine]rhodium nonasodium salt.

[0012] The present disclosure also provides a hydroformylation process for making 2- (octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I). The process comprises: contacting Compound IV with carbon monoxide and hydrogen in a reaction zone in the presence of a homogeneous rhodium catalyst to form a product mixture comprising Compound I, wherein the homogeneous rhodium catalyst comprises triphenyl phosphite (P(OC6H5)3) as ligand.

[0013] The present disclosure also provides a compound of structural formula (III) in the form of any one of its stereoisomers or a mixture thereof.

[0014] The present disclosure also provides a mixture of 2-(octahydro-1 H-4,7- methanoinden-5-yl)acetaldehyde (Compound I), 6- methyloctahydro- 1 H-4, 7- methanoindene-5-carbaldehyde (Compound II) and 5-methyloctahydro-1 H-4,7- methanoindene-5-carbaldehyde (Compound III), as well as fragrance compositions or consumer products comprising such mixture.

[0015] DETAILED DESCRIPTION IFF-10187-WO-PCT

[0016] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.

[0017] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, composition, compound, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, composition, compound, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0018] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0020] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints IFF-10187-WO-PCT thereof, and all integers and fractions within the range. For example, when a range of "1 to 10" is recited, the recited range should be construed as including ranges “1 to 8”, “3 to 10”, “2 to 7”, “1.5 to 6”, “3.4 to 7.8”, “1 to 2 and 7-10”, “2 to 4 and 6 to 9”, “1 to 3.6 and 7.2 to 8.9”, “1-5 and 10”, “2 and 8 to 10”, “1.5-4 and 8”, and the like.

[0021] While compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods also can “consist essentially of” or “consist of” the various components or steps, unless stated otherwise.

[0022] Some of the compounds of the present disclosure have stereoisomers. Unless explicitly indicated, a compound of the present disclosure includes its stereoisomers and any combinations or mixtures of the stereoisomers.

[0023] Before addressing details of embodiments described below, some terms are defined or clarified.

[0024] The term “Compound I”, as used herein, is the chemical compound named 2- (octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde and represented by the following structural formula (I):

[0025] The term “Compound II”, as used herein, is the chemical compound named 6- methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde and represented by the following structural formula (II):

[0026] The term “Compound III”, as used herein, is the chemical compound named 5- methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde and represented by the following structural formula (III): IFF-10187-WO-PCT

[0027] The term “Compound IVa”, as used herein, is the chemical compound named 5- methyleneoctahydro-1 H-4,7-methanoindene and represented by the following structural formula (IVa). The term “Compound IVb”, as used herein, is the chemical compound named 5-methyl-2,3,3a,4,7,7a-hexahydro-1 H-4,7-methanoindene and represented by the following structural formula (IVb). Compound IVa and Compound IVb are collectively referred to as Compound IV represented by the following structural formula (IV) wherein one of the symbols --- is a single bond and the other is a double bond.

[0028] The term “mol%”, as used herein, means percentage by mole. The term “wt%”, as used herein, means percentage by weight. As used herein, the terms “kg”, “g”, and “mg” refer to “kilogram”, “gram”, and “milligram” respectively. The terms “L”, “mL” and “pL” refer to “liter”, “milliliter” and “microliter” respectively. The terms “mM” and “M” refer to molar concentration units “millimolar” (mmol / L) and “molar” (mol / L) respectively.

[0029] The present disclosure provides a hydroformylation process for making 2- (octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I). The process comprises: contacting Compound IV with carbon monoxide (CO) and hydrogen (H2) in a reaction zone in the presence of a cobalt catalyst to form a product mixture comprising Compound I, wherein the cobalt catalyst is (i) dicobalt octacarbonyl (Co2(CO)8) or (ii) a mixture of dicobalt octacarbonyl and a cobalt compound selected from the group of cobalt(ll) acetyl acet on ate (Co(acac)2), cobalt(lll) acetyl acet on ate (Co(acac)s), cobalt(ll) acetate (Co(OAc)2), cobalt(ll) hydroxide (Co(OH)2), mixtures of cobalt(ll) chloride (C0O2) and an alkali metal carbonate, and combinations thereof. In some embodiments, the cobalt catalyst is a homogeneous catalyst. In some embodiments, the product mixture further comprises 6-methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde (Compound II). In some embodiments, the product mixture further comprises 5- methyloctahydro- 1 H- 4,7-methanoindene-5-carbaldehyde (Compound III).

[0030] In some embodiments, Compound IV comprises or is a mixture of Compound IVa and Compound IVb, and the product mixture comprises Compound I, Compound II and Compound III. In some embodiments, the mole ratio of Compound IVa to Compound IVb IFF-10187-WO-PCT in the mixture is at least 1 :1 , 1.5:1 , 2:1 , 3:1 , 4:1 , 5:1 , 6:1 , 7:1 , 8:1 , 9:1 , 10:1 , 11 :1 , 12:1 , or 13:1. In some embodiments, the mole ratio of Compound IVa to Compound IVb in the mixture is no more than 200:1 , 100:1 , 50:1 , or 20:1. In some embodiments, the amount of Compound I in the product mixture is at least 50 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, or 80 mol%, based on the total mole amount of Compounds I, II and III. Without being bound by theory it is believed that in the hydroformylation reaction, Compound IVa produces Compound I and Compound III, and Compound IVb produces Compound II and Compound III. In some embodiments, the yield of Compound I is at least 50%, 60%, 65%, 70%, 75%, or 80%, based on the Compound IVa starting material.

[0031] A syngas (i.e., mixture of carbon monoxide (CO) and hydrogen (H2)) is used in the hydroformylation process. In some embodiments, the mole ratio of carbon monoxide to hydrogen is at least 0.5:1 , 0.8:1 , 0.9:1 , 1 :1 , 1.1 :1 , 1 .2:1 , or 1 .5:1 . In some embodiments, the mole ratio of carbon monoxide to hydrogen is no more then 4:1 , 3:1 , 2:1 , 1.5:1 , 1.2:1 , or 1.1 :1.

[0032] In some embodiments, the cobalt catalyst is dicobalt octacarbonyl (Co2(CO)8). In some embodiments, the amount of dicobalt octacarbonyl fed into the reaction zone is at least 0.01 mol%, 0.02 mol%, 0.05 mol%, 0.1 mol%, 0.2 mol%, or 0.5 mol%, based on the amount of Compound IV fed into the reaction zone. In some embodiments, the amount of dicobalt octacarbonyl fed into the reaction zone is no more than 10 mol%, 5 mol%, 2 mol%, 1.5 mol%, or 1 mol%, based on the amount of Compound IV fed into the reaction zone.

[0033] In some embodiments, the cobalt catalyst is a mixture of dicobalt octacarbonyl and a cobalt compound selected from the group of cobalt(ll) acetyl acet on ate (Co(acac)2), cobalt(lll) acetyl acet on ate (Co(acac)s), cobalt(ll) acetate (Co(OAc)2), cobalt(ll) hydroxide (Co(OH)2), mixtures of cobalt(ll) chloride (C0O2) and an alkali metal carbonate, and combinations thereof. In some embodiments, the alkali metal is sodium (Na) or potassium (K). In some embodiments, the mole ratio of cobalt(ll) chloride to alkali metal carbonate is in a range of from about 1 :0.5 to about 1 :4, or from about 1 :1 to about 1 :3. In some embodiments, the mole ratio of cobalt(ll) chloride to alkali metal carbonate is at least 1 :0.5, 1 :0.8, 1 :1 , 1 :1 .5, or 1 :2. In some embodiments, the mole ratio IFF-10187-WO-PCT of cobalt(ll) chloride to alkali metal carbonate is no more than 1 :20, 1 :10, 1 :5, 1 :4, 1 :3, or 1 :2.

[0034] In some embodiments, the amount of dicobalt octacarbonyl fed into the reaction zone is at least 0.0002 mol%, 0.0005 mol%, 0.001 mol%, 0.002 mol%, 0.005 mol%, 0.006 mol%, 0.007 mol%, 0.008 mol%, or 0.009 mol%, based on the amount of Compound IV fed into the reaction zone. In some embodiments, the amount of dicobalt octacarbonyl fed into the reaction zone is no more than 0.5 mol%, 0.2 mol%, 0.1 mol%, 0.05 mol%, 0.04 mol%, 0.03 mol%, 0.02 mol%, 0.015 mol%, 0.012 mol%, or 0.01 mol%, based on the amount of Compound IV fed into the reaction zone. In some embodiments, the amount of cobalt compound fed into the reaction zone is at least 0.002 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.05 mol%, 0.1 mol%, 0.15 mol%, or 0.2 mol%, based on the amount of Compound IV fed into the reaction zone. In some embodiments, the amount of cobalt compound fed into the reaction zone is no more than 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.8 mol%, 0.5 mol%, or 0.2 mol%, based on the amount of Compound IV fed into the reaction zone. In some embodiments, the mole ratio of dicobalt octacarbonyl to the cobalt compound is in a range of from 1 :1 to 1 :100, or from 1 :5 to 1 :50, or from 1 :10 to 1 :25. With respect to the mixture of cobalt(ll) chloride and an alkali metal carbonate, the amount of cobalt compound refers to the amount of cobalt(ll) chloride, and the mole ratio of dicobalt octacarbonyl to the cobalt compound refers to the mole ratio of dicobalt octacarbonyl to cobalt(ll) chloride.

[0035] In some embodiments, the cobalt compound is selected from the group of cobalt(ll) acetyl acet on ate (Co(acac)2), cobalt(lll) acetyl acet on ate (Co(acac)s), cobalt(ll) acetate (Co(OAc)2), and combinations thereof. In some embodiments, the cobalt compound comprises or is cobalt(ll) acetyl acet on ate and / or cobalt(ll) acetate. In some embodiments, the cobalt compound comprises or is cobalt(ll) acetylacetonate. In some embodiments, the cobalt compound comprises or is cobalt(ll) acetate.

[0036] In some embodiments, the hydroformylation reaction is carried out in the presence of a solvent. In some embodiments, the solvent is selected from the group of toluene, ethylbenzene, xylene, and combinations thereof. In some embodiments, the amount of the solvent present in the reaction zone is at least 30 wt%, 40 wt%, 50 wt%, 60 wt%, or 70 wt%, based on the total weight of the reaction mixture. In some embodiments, the amount IFF-10187-WO-PCT of the solvent present in the reaction zone is no more than 98 wt%, 97 wt%, 96 wt%, 95 wt%, 92 wt%, 90 wt%, or 85 wt%, based on the total weight of the reaction mixture.

[0037] In some embodiments, the hydroformylation reaction is carried out in substantial absence of a solvent. In some embodiments, the amount of the solvent present in the reaction zone is no more than 10 wt%, 5 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.2 wt%, or 0.1 wt%, based on the total weight of the reaction mixture.

[0038] In some embodiments, the hydroformylation reaction is carried out in the presence of a ligand such as triphenylphosphine oxide (TPPO). In some embodiments, the mole ratio of dicobalt octacarbonyl to the ligand is in a range of from 1 :1 to 1 :3, or from 1 :2 to 1 :2.5. In some embodiments, the reaction zone is substantially free or free of the ligand. In some embodiments, the amount of the ligand present in the reaction zone is no more than 20 mol%, 10 mol%, 5 mol%, 2 mol%, 1 mol%, 0.5 mol%, 0.2 mol%, or 0.1 mol%, based on the molar amount of dicobalt octacarbonyl.

[0039] In some embodiments, the hydroformylation reaction temperature is in a range of from about 100eC to about 140eC, or from about 120eC to about 130eC. In some embodiments, the hydroformylation reaction temperature is at least 70eC, 80eC, 90eC, 95eC, 100eC, 105eC, 110eC, 115eC, or 120eC. In some embodiments, the hydroformylation reaction temperature is no more than 180eC, 170eC, 160eC, 150eC, 145eC, 140eC, 135eC, or 130eC. In some embodiments, the hydroformylation reaction can be carried out under 200-900 psig (pounds per square inch gauge) of syngas, or 200-800 psig of syngas, or 300-700 psig of syngas, or 400-750 psig of syngas, or 450-700 psig of syngas. When the catalyst is dicobalt octacarbonyl, the reaction time is at least 2 hrs, 5 hrs, 8 hrs, 10 hrs, 11 hrs, or 12 hrs and in some embodiments no more than 72 hrs, 48 hrs, 36 hrs, 24 hrs, 20 hrs, 18 hrs, or 16 hrs. When the catalyst is a mixture of dicobalt octacarbonyl and a cobalt compound, the reaction time is at least 5 hrs, 10 hrs, 12 hrs, 14 hrs, 15 hrs, 16 hrs, or 17 hrs and in some embodiments no more than 72 hrs, 48 hrs, 36 hrs, 30 hrs, 24 hrs, 22 hrs, 20 hrs, or 18 hrs. In some embodiments, the process further comprises recovering Compound I and optionally Compound II and / or Compound III from the product mixture at the end of the reaction. Compounds I, II and / or III can be separated and recovered by methods known in the art such as crystallization, distillation and chromatography. IFF-10187-WO-PCT

[0040] The present disclosure also provides a hydroformylation process for making 2- (octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I). The process comprises: (a) contacting Compound IV with carbon monoxide and hydrogen in a reaction zone in the presence of a heterogeneous rhodium catalyst to form a product mixture comprising Compound I, wherein the heterogeneous rhodium catalyst comprises or is carbonyl(hydro)tris[tris(3-sulfophenyl)phosphine]rhodium nonasodium salt (RhH(CO)(TPPTS)s). The rhodium catalyst carbonyl(hydro)tris[tris(3- sulfophenyl)phosphine]rhodium nonasodium salt has the formula RhH(CO)(TPPTS)s and CAS # 109427-00-1. TPPTS is triphenylphosphine-3,3’,3”-trisulfonic acid trisodium salt having the formula P(C6H4SO3Na)3.

[0041] In some embodiments, the product mixture further comprises 6-methyloctahydro- 1 H-4,7-methanoindene-5-carbaldehyde (Compound II). In some embodiments, essentially no Compound III (5-methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde) is generated in step (a) or the hydroformylation process using the heterogeneous rhodium catalyst. In some embodiments, the yield of Compound III in step (a) or the hydroformylation process is less than 2%, 1%, 0.5%, 0.2%, 0.1%, 0.05%, 0.02%, or 0.01%.

[0042] In some embodiments, the process further comprises contacting a rhodium catalyst precursor with TPPTS in the presence of carbon monoxide and hydrogen in the reaction zone to form the heterogeneous rhodium catalyst in situ before or during the hydroformylation step (a). In some embodiments, the rhodium catalyst precursor is selected from the group of rhodium(lll) trichloride (RhC ), (acetylacetonato)dicarbonylrhodium(l) (Rh(acac)(CO)2), and combinations thereof. Rha3includes anhydrous and hydrated ones (e.g., rhodium(lll) trichloride trihydrate). In some embodiments, the mole ratio of TPPTS to the rhodium catalyst precursor fed into the reaction zone is at least 1 :1 , 2:1 , 3:1 , 4:1 , 5:1 , 6:1 , 7:1 , 8:1 , 10:1 , 12:1 , or 15:1. In some embodiments, the mole ratio of TPPTS to the rhodium catalyst precursor fed into the reaction zone is no more than 200:1 , 100:1 , 50:1 , 40:1 , 30:1 , or 20:1 .

[0043] In some embodiments, the heterogeneous rhodium catalyst is recovered and reused. In such embodiments, the hydroformylation process further comprises: (b) recovering the rhodium catalyst from the product mixture; and (c) reusing the recovered rhodium catalyst in the hydroformylation step (a). In some embodiments, the rhodium IFF-10187-WO-PCT catalyst can be recovered from the product mixture by filtration before recovering Compound I and optionally Compound II from the product mixture at the end of the reaction.

[0044] In some embodiments, Compound IV comprises or is a mixture of Compound IVa and Compound IVb, and the product mixture comprises Compound I and Compound II. In some embodiments, the mole ratio of Compound IVa to Compound IVb in the mixture is at least 1 :1 , 1.5:1 , 2:1 , 3:1 , 4:1 , 5:1 , 6:1 , 7:1 , 8:1 , 9:1 , 10:1 , 11 :1 , 12:1 , or 13:1. In some embodiments, the mole ratio of Compound IVa to Compound IVb in the mixture is no more than 200:1 , 100:1 , 50:1 , or 20:1 . In some embodiments, the amount of Compound I in the product mixture is at least 60 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, or 90 mol%, based on the total mole amount of Compounds I and II. Without being bound by theory it is believed that in the hydroformylation reaction, Compound IVa produces Compound I, and Compound IVb produces Compound II. In some embodiments, the yield of Compound I is at least 50%, 55%, 60%, 65%, 70%, or 75%, based on the Compound IVa starting material.

[0045] A syngas (i.e., mixture of carbon monoxide (CO) and hydrogen (H2)) is used in the hydroformylation process. In some embodiments, the mole ratio of carbon monoxide to hydrogen is at least 0.5:1 , 0.8:1 , 0.9:1 , 1 :1 , 1 .1 :1 , 1 .2:1 , or 1 .5:1 . In some embodiments, the mole ratio of carbon monoxide to hydrogen is no more then 4:1 , 3:1 , 2:1 , 1.5:1 , 1.2:1 , or 1.1 :1.

[0046] In some embodiments, the amount of the rhodium catalyst RhH(CO)(TPPTS)s present in the reaction zone is at least 0.001 mol%, 0.002 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, or 0.03 mol%, based on the amount of Compound IV fed into the reaction zone. In some embodiments, the amount of the rhodium catalyst RhH(CO)(TPPTS)s present in the reaction zone is no more than 0.4 mol%, 0.3 mol%, 0.2 mol%, 0.1 mol%, or 0.05 mol%, based on the amount of Compound IV fed into the reaction zone.

[0047] In some embodiments, the hydroformylation reaction (with heterogeneous rhodium catalyst) is carried out in the presence of a solvent. In some embodiments, the solvent is selected from the group of methanol, ethanol, propanol, isopropanol, formamide, methyl tert-butyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran, and combinations thereof. In some embodiments, the amount of the solvent present in the IFF-10187-WO-PCT reaction zone is at least 20 wt%, 30 wt%, 40 wt%, 50 wt%, or 60 wt%, based on the total weight of the reaction mixture. In some embodiments, the amount of the solvent present in the reaction zone is no more than 98 wt%, 97 wt%, 96 wt%, 95 wt%, 92 wt%, 90 wt%, or 85 wt%, based on the total weight of the reaction mixture.

[0048] In some embodiments, the hydroformylation reaction temperature (with heterogeneous rhodium catalyst) is in a range of from about 60eC to about 140eC, or from about 70eC to about 130eC, or from about 80eC to about 120eC. In some embodiments, the hydroformylation reaction temperature is at least 50eC, 60eC, 65eC, 70eC, 75eC, 80eC, or 85eC. In some embodiments, the hydroformylation reaction temperature is no more than 140eC, 130eC, 125eC, 120eC, 115eC, or 110eC. In some embodiments, the hydroformylation reaction can be carried out under 200-900 psi (pounds per square inch) of syngas, or 200-800 psi of syngas, or 250-700 psi of syngas, or 250-600 psi of syngas, or 250-500 psi of syngas. In some embodiments, the reaction time is at least 3 hrs, 4 hrs, 5 hrs, 6 hrs, 7 hrs, or 8 hrs and in some embodiments no more than 72 hrs, 48 hrs, 36 hrs, 24 hrs, 20 hrs, 18 hrs, or 16 hrs. In some embodiments, the process further comprises recovering Compound I and optionally Compound II from the product mixture at the end of the reaction. Compounds I and II can be separated and recovered by methods known in the art such as crystallization, distillation and chromatography.

[0049] The present disclosure also provides a hydroformylation process for making 2- (octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I). The process comprises: contacting Compound IV with carbon monoxide and hydrogen in a reaction zone in the presence of a homogeneous rhodium catalyst to form a product mixture comprising Compound I, wherein the homogeneous rhodium catalyst comprises triphenyl phosphite (P(OC6H5)3) as ligand. It has been surprisingly discovered that the homogeneous rhodium catalyst comprising triphenyl phosphite as ligand can speed up the hydroformylation reaction more effectively than other similar homogeneous rhodium catalysts. In some embodiments, the homogeneous rhodium catalyst comprises one, two, or three triphenyl phosphite ligand(s) bound to the central Rh(l). In some embodiments, the homogeneous rhodium catalyst further comprises hydrogen atom and carbon monoxide bound to the central Rh (I). IFF-10187-WO-PCT

[0050] In some embodiments, the product mixture further comprises 6-methyloctahydro- 1 H-4,7-methanoindene-5-carbaldehyde (Compound II). In some embodiments, essentially no Compound III (5-methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde) is generated in the hydroformylation process using the homogeneous rhodium catalyst. In some embodiments, the yield of Compound III in the hydroformylation process is less than 2%, 1%, 0.5%, 0.2%, 0.1%, 0.05%, 0.02%, or 0.01%.

[0051] In some embodiments, the process further comprises contacting a rhodium catalyst precursor with triphenyl phosphite in the presence of a solvent, carbon monoxide and hydrogen in the reaction zone to form the homogeneous rhodium catalyst in situ before or during the hydroformylation reaction. In some embodiments, the solvent is selected from the group of methanol, ethanol, propanol, isopropanol, formamide, and combinations thereof. In some embodiments, the solvent comprises or is methanol. In some embodiments, the solvent (e.g., methanol) is substantially free of oxygen (O2). By “substantially free of oxygen” means the amount of oxygen present or dissolved in the solvent is no more than 5 mM , 2 mM , 1 mM , 0.5 mM , 0.2 mM, 0.1 mM , or 0.05 mM , based on the volume amount of the solvent. In some embodiments, the rhodium catalyst precursor is selected from the group of rhodium(lll) trichloride (RhCls), (acetylacetonato)dicarbonylrhodium(l) (Rh(acac)(CO)2), and combinations thereof. RhCls includes anhydrous and hydrated ones (e.g., rhodium(lll) trichloride trihydrate). In some embodiments, the mole ratio of triphenyl phosphite to the rhodium catalyst precursor fed into the reaction zone is at least 1 :1 , 2:1 , 3:1 , 3.5:1 , 4:1 , 4.5:1 , 5:1 , or 6:1. In some embodiments, the mole ratio of triphenyl phosphite to the rhodium catalyst precursor fed into the reaction zone is no more than 50:1 , 40:1 , 30:1 , 20:1 , 15:1 , 12:1 , 10:1 , 8:1 , 7:1 , 6:1 , or 5:1.

[0052] In some embodiments, Compound IV comprises or is a mixture of Compound IVa and Compound IVb, and the product mixture comprises Compound I and Compound II. In some embodiments, the mole ratio of Compound IVa to Compound IVb in the mixture is at least 1 :1 , 1.5:1 , 2:1 , 3:1 , 4:1 , 5:1 , 6:1 , 7:1 , 8:1 , 9:1 , 10:1 , 11 :1 , 12:1 , or 13:1. In some embodiments, the mole ratio of Compound IVa to Compound IVb in the mixture is no more than 200:1 , 100:1 , 50:1 , or 20:1 . In some embodiments, the amount of Compound I in the product mixture is at least 60 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, or 90 IFF-10187-WO-PCT mol%, based on the total mole amount of Compounds I and II. Without being bound by theory it is believed that in the hydroformylation reaction, Compound IVa produces Compound I, and Compound IVb produces Compound II. In some embodiments, the yield of Compound I is at least 55%, 60%, 65%, 70%, 75%, or 80%, based on the Compound IVa starting material.

[0053] A syngas (i.e., mixture of carbon monoxide (CO) and hydrogen (H2)) is used in the hydroformylation process. In some embodiments, the mole ratio of carbon monoxide to hydrogen is at least 0.5:1 , 0.8:1 , 0.9:1 , 1 :1 , 1 .1 :1 , 1 .2:1 , or 1 .5:1 . In some embodiments, the mole ratio of carbon monoxide to hydrogen is no more then 4:1 , 3:1 , 2:1 , 1.5:1 , 1.2:1 , or 1.1 :1.

[0054] In some embodiments, the amount of the homogeneous rhodium catalyst present in the reaction zone is in a range of from about 0.0006 mol% to about 0.02 mol%, or from about 0.0008 mol% to about 0.01 mol%, or from about 0.001 mol% to about 0.008 mol%, or from about 0.002 mol% to about 0.006 mol%, based on the amount of Compound IV fed into the reaction zone. In some embodiments, the amount of the homogeneous rhodium catalyst present in the reaction zone is at least 0.0002 mol%, 0.0004 mol%, 0.0006 mol%, 0.0008 mol%, 0.001 mol%, 0.002 mol%, 0.003 mol%, 0.004 mol%, 0.005 mol%, or 0.006 mol%, based on the amount of Compound IV fed into the reaction zone. In some embodiments, the amount of the homogeneous rhodium catalyst present in the reaction zone is no more than 0.2 mol%, 0.1 mol%, 0.05 mol%, 0.02 mol%, 0.01 mol%, 0.008 mol%, 0.007 mol%, 0.006 mol%, 0.005 mol%, 0.004 mol%, or 0.003 mol%, based on the amount of Compound IV fed into the reaction zone.

[0055] In some embodiments, the hydroformylation reaction (with homogeneous rhodium catalyst) is carried out in the presence of a solvent. In some embodiments, the solvent is selected from the group of methanol, ethanol, propanol, isopropanol, formamide, and combinations thereof. In some embodiments, the solvent comprises or is methanol. In some embodiments, the amount of the solvent present in the reaction zone is at least 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, or 0.5 wt%, based on the total weight of the reaction mixture. In some embodiments, the amount of the solvent present in the reaction zone is no more than 30 wt%, 20 wt%, 10 wt%, 5 wt%, or 2 wt%, based on the total weight IFF-10187-WO-PCT of the reaction mixture. It has been surprisingly discovered that a small amount of solvent (e.g., methanol) can significantly increase the reaction rate of the hydroformylation reaction.

[0056] In some embodiments, the hydroformylation reaction temperature (with homogeneous rhodium catalyst) is in a range of from about 60eC to about 140eC, or from about 70eC to about 130eC, or from about 80eC to about 120eC. In some embodiments, the hydroformylation reaction temperature is at least 50eC, 60eC, 65eC, 70eC, 75eC, 80eC, 85eC, or 90eC. In some embodiments, the hydroformylation reaction temperature is no more than 140eC, 130eC, 125eC, 120eC, 115eC, or 110eC. In some embodiments, the hydroformylation reaction can be carried out under 200-900 psi (pounds per square inch) of syngas, or 200-800 psi of syngas, or 250-700 psi of syngas, or 250-600 psi of syngas, or 250-500 psi of syngas. In some embodiments, the reaction time is at least 3 hrs, 4 hrs, 5 hrs, 6 hrs, 7 hrs, or 8 hrs. In some embodiments, the reaction time is no more than 72 hrs, 48 hrs, 36 hrs, 24 hrs, 20 hrs, 18 hrs, 16 hrs, 14 hrs, 12 hrs, or 10 hrs. In some embodiments, the process further comprises recovering Compound I and optionally Compound II from the product mixture at the end of the reaction. Compounds I and II can be separated and recovered by methods known in the art such as crystallization, distillation and chromatography.

[0057] The present disclosure also provides a compound of structural formula (III) in the form of any one of its stereoisomers or a mixture thereof. Compound III can be made by the hydroformylation processes described in this disclosure using Compound IV as the starting material. Compound III can be a component present in a fragrance composition.

[0058] The present disclosure also provides a mixture of Compound I, Compound II and Compound III. In some embodiments, the amount of Compound I is in a range of from about 50 mol% to about 95 mol%, or from about 60 mol% to about 92 mol%, or from about 70 mol% to about 90 mol%, or from about 75 mol% to about 88 mol%, based on the total mole amount of Compounds I, II and III. In some embodiments, the amount of Compound II is in a range of from about 5 mol% to about 30 mol%, or from about 7 mol% to about 25 mol%, or from about 8 mol% to about 20 mol%, based on the total mole amount of Compounds I, II and III. In some embodiments, the amount of Compound III is in a range of from about 1 mol% to about 10 mol%, or from about 2 mol% to about 8 mol%, IFF-10187-WO-PCT or from about 3 mol% to about 7 mol%, based on the total mole amount of Compounds I, II and III.

[0059] Compound I, Compound II, Compound III, and their mixtures can be used in perfumery products, including the preparation of perfumes and colognes, the perfuming of personal care products such as soaps, shower gels, and hair care products, fabric care products, air fresheners, and cosmetic preparations. They can also be used to perfume cleaning agents such as detergents, dishwashing materials, scrubbing compositions, and window cleaners.

[0060] The present disclosure also provides a fragrance composition comprising an olfactory acceptable amount of a mixture of Compound I, Compound II and Compound III described in this disclosure. Olfactory acceptable amount is understood to mean the amount of compound in fragrance composition the individual component will contribute to its particular olfactory characteristics, but the olfactory effect of the fragrance composition will be the sum of the effects of each of the fragrance ingredients. In some embodiments, the fragrance composition further comprises a product selected from the group of a perfume, a cologne, a toilet water, a cosmetic product, a personal care product, a fabric care product, a cleaning product, and an air freshener. In some embodiments, the olfactory acceptable amount is in a range of from about 0.005 wt% to about 50 wt%, or from about 0.5 wt% to about 25 wt%, or from about 1 wt% to about 10 wt%, based on the total weight of the fragrance composition. When used in a fragrance composition, the mixture of Compounds I, II and III provides fruity, sweet, and green notes to make the fragrance composition more desirable and noticeable, and add the perception of value.

[0061] The present disclosure also provides a consumer product comprising a mixture of Compound I, Compound II and Compound III described in this disclosure. In some embodiments, the consumer product is selected from the group of perfumes, colognes, personal care products (e.g., soaps, shower gels, hair care products), fabric care products, air fresheners, cosmetic preparations, and cleaning agents (e.g., detergents, dishwashing materials, scrubbing compositions, window cleaners).

[0062] Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that IFF-10187-WO-PCT other aspects and embodiments are possible without departing from the scope of the invention.

[0063] EXAM PLES

[0064] The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.

[0065] General

[0066] Unless otherwise specified, the starting material Compound IV is a mixture of Compound IVa and Compound IVb, and the mole ratio of Compound IVa to Compound IVb in the mixture is 93:7; syngas is a mixture of carbon monoxide (CO) and hydrogen (H2) with mole ratio of 1 :1 .

[0067] Example 1 : Preparation of Compounds I, II and III with Dicobalt Octacarbonyl

[0068] A 2 L autoclave was charged with Compound IV (400 g, 0.27 mol), dicobalt octacarbonyl (0.92 g, 0.0027 mol), triphenylphosphine oxide (1.65 g, 0.006 mol) and toluene (400 g). The autoclave was flushed and vented three times with nitrogen followed three times with syngas. The autoclave was subsequently pressurized to 580 psig with syngas and heated to 120 °C. Gas-liquid chromatography (GLC) analysis of a reaction mixture aliquot indicated the completion of the reaction after 14 hours. The reaction mixture was then cooled down to 25 °C, vented and purged three times with nitrogen to provide a crude product mixture which was treated with 20 wt% acetic acid solution for 2 hours at 25 °C. The product mixture was then washed with water and finally with 5 wt% sodium carbonate solution. The resulting product mixture was distilled to generate a mixture of Compounds I, II and III (330 g, 85% total yield) containing 80 mol% Compound I, 15 mol% Compound II and 5 mol% Compound III based on the total amounts of Compounds I, II and III. Compounds I, II and III can be separated by GC and characterized by NMR.1H-NMR characteristics of Compound I is shown below:

[0069] 1H-NM R (CDO3, 500 MHz): 9.76 ppm (t, about 33% of 1 H, J=2.1 Hz), 9.73 ppm (t, about 66% of 1 H, J=2.1 Hz), 0.85-2.52 (m, 16.66H), 0.57 ppm (m, about 33% of 1 H).

[0070] 1H-NM Rcharacteristics of Compound II is shown below: IFF-10187-WO-PCT

[0071] 1H-NM R (CDCI3, 500 MHz): 9.65 ppm (d, 1 H, J=2.0 Hz), 1.01 ppm (d, 3H, J=7.0 Hz), 0.90-

[0072] 2.25 ppm (m, 14H).

[0073] 1H-NM Rcharacteristics of Compound III is shown below:

[0074] 1H-NM R (CDCI3, 500 MHz): 9.41 ppm (s, 1 H), 2.21 ppm (m, 1 H), 2.08 ppm (dd, 1 H, J=4.7,

[0075] 12.4 Hz), 1.95 ppm (s, 1 H), 1.91 ppm (d, 1 H, J=4.5 Hz), 1.74-1.85 ppm (m, 4H), 1.60 ppm

[0076] (dd, 1 H, J=6.4, 11.8 Hz), 1.26 ppm (m, 1 H, J=2.7, 11 .0 Hz), 1.13 ppm (dt, 1 H, J=6.4 Hz), 1.02 ppm (s, 3H), 0.83-0.98 ppm (m, 2H), 0.65 ppm (dd, 1 H, J=2.8, 12.4 Hz).

[0077] A 2 L autoclave was charged with Compound IV (400 g, 0.27 mol), dicobalt octacarbonyl (0.46 g, 0.0013 mol) and toluene (200 g). The autoclave was flushed and vented three times with nitrogen followed three times with syngas. The autoclave was subsequently pressurized to 580 psig with syngas and heated to 120 °C. Gas- liquid chromatography (GLC) analysis of a reaction mixture aliquot indicated the completion of the reaction after 20 hours. The reaction mixture was then cooled down to 25 °C, vented and purged three times with nitrogen to provide a crude product mixture which was treated with 20 wt% acetic acid solution for 2 hours at 25 °C. The product mixture was then washed with water and finally with 5 wt% sodium carbonate solution. The resulting product mixture was distilled to generate a mixture of Compounds I, II and III (322 g, 83% total yield) containing 83 mol% Compound I, 13 mol% Compound II and 4 mol%

[0078] Compound III based on the total amounts of Compounds I, II and III. Compounds I, II and

[0079] III can be separated by GC and characterized by NM R

[0080] I, II and III with a Mixture of Dicobalt

[0081] A 100 mL stainless steel Parr reactor equipped with one glass inner liner and a magnetic stirrer was charged with cobalt(ll) acetyl acet on ate (0.015 mmol), dicobalt octacarbonyl (0.0015 mmol), toluene (2.5 mL), Compound IV (15 mmol) and 850 * L of dodecane as internal standard. The reactor was then purged three times with syngas before pressurized to 40 bar with syngas. The reactor was heated to 120 °C and stirred overnight. After 17 hours, the reaction was complete, the reactor was cooled to 0 °C for 45 IFF-10187-WO-PCT minutes, and excess gas was vented off in a well-ventilated fume-hood. A sample of product mixture was then filtered through a plug of celite, washed with dicloromethane, and analyzed by1H-NM R and GC-FID (gas chromatography-flame ionization detector). The total yield of Compounds I, II and III is 84%. Example 4: Preparation of Compounds I, II and III with a Mixture of Dicobalt Octacarbonyl and a Cobalt Compound

[0082] A 100 mL stainless steel Parr reactor equipped with one glass inner liner and a magnetic stirrer was charged with a cobalt compound (0.0375 mmol) indicated in Table 1 , dicobalt octacarbonyl (0.0015 mmol), toluene (7.5 mL), Compound IV (15 mmol) and 850 • L of dodecane as internal standard. The reactor was then purged three times with syngas before pressurized to 50 bar with syngas. The reactor was heated to 130 °C and stirred overnight. After 17 hours, the reaction was complete, the reactor was cooled to 0 °C for 45 minutes, and excess gas was vented off in a well-ventilated fume-hood. A sample of product mixture was then filtered through a plug of celite, washed with dicloromethane, and analyzed by1H-NM R and GC-FID. The conversion rate of starting material (Compound IV), total yield of Compounds I and II, and yield of Compound III are presented in Table 1 .

[0083] Table 1 IFF-10187-WO-PCT

[0084] Note: C0CI2 + ^CO3a: the cobalt compound is a mixture of C0CI2 (0.0375 mmol) and K2CO3 (0.075 mmol); Conv means conversion; Yieldbis the total yield of Compounds I and II; Yield0is the yield of Compound III. Rhodium

[0085] A 2 L autoclave was charged with Compound IV (188 g, 1268 mmol), triphenylphosphine-3,3’,3”-trisulfonic acid trisodium salt (5.95 g, 10.15 mmol), rhodium(lll) trichloride trihydrate (0.133 g, 0.507 mmol), sodium bicarbonate (0.213 g, 2.54 mmol), and degassed methanol (250 mL). The autoclave was flushed and vented three times with nitrogen and twice with syngas. The autoclave was then pressurized to 294 psi with syngas and heated to 90 °C. Gas-liquid chromatography (GLC) analysis of a reaction mixture aliquot indicated the completion of the reaction after 14 hours. The reaction mixture was then cooled down to 25 °C, vented and purged three times with nitrogen to provide a crude product mixture which was concentrated under vacuum to remove the methanol. The product mixture was then centrifugated to separate the upper colorless product phase from the lower solid rhodium catalyst phase. The recovered rhodium catalyst can be reused for another hydroformylation reaction of Compound IV. The separated product phase was purified by fractional distillation to generate a mixture of Compounds I and II (151.4 g, 67% total yield) containing 94 mol% Compound I and 6 mol% Compound II based on the total amounts of Compounds I and II. Rhodium

[0086] A 2 L autoclave was charged with Compound IV (188 g, 1268 mmol), triphenylphosphine-3,3’,3”-trisulfonic acid trisodium salt (5.95 g, 10.15 mmol), (acetylacetonato)dicarbonylrhodium(l) (0.131 g, 0.507 mmol), and degassed methanol (250 mL). The autoclave was flushed and vented three times with nitrogen and twice with syngas. The autoclave was then pressurized to 294 psi with syngas and heated to 90 °C. Gas-liquid chromatography (GLC) analysis of a reaction mixture aliquot indicated the completion of the reaction after 7.5 hours. The reaction mixture was then cooled down to 25 °C, vented and purged three times with nitrogen to provide a crude product mixture which was concentrated under vacuum to remove the methanol. The product mixture was IFF-10187-WO-PCT then centrifugated to separate the upper colorless product phase from the lower solid rhodium catalyst phase. The recovered rhodium catalyst can be reused for another hydroformylation reaction of Compound IV. The separated product phase was purified by fractional distillation to generate a mixture of Compounds I and II (171.2 g, 76% total yield) containing 92 mol% Compound I and 8 mol% Compound II based on the total amounts of Compounds I and II. Rhodium

[0087] A 2 L autoclave was charged with Compound IV (1100 g, 7420 mmol), triphenyl phosphite (0.368 g, 1.187 mmol), (acetylacetonato)dicarbonylrhodium(l) (0.077 g, 0.298 mmol) and degassed methanol (15 mL). The autoclave was flushed and vented three times with nitrogen and twice with syngas. The autoclave was then pressurized to 310 psi with syngas and heated to 95 °C. Gas-liquid chromatography (GLC) analysis of a reaction mixture aliquot indicated the completion of the reaction after 9 hours. The reaction mixture was then cooled down to 25 °C, vented and purged three times with nitrogen to provide a crude product mixture. The crude product mixture was purified by fractional distillation to generate a mixture of Compounds I and II (1110 g, 84% total yield) containing 87 mol% Compound I and 13 mol% Compound II based on the total amounts of Compounds I and II.

[0088] A 2 L autoclave was charged with Compound IV (1100 g, 7420 mmol), triphenyl phosphine (0.311 g, 1.187 mmol), (acetylacetonato)dicarbonylrhodium(l) (0.077 g, 0.298 mmol) and degassed methanol (15 mL). The autoclave was flushed and vented three times with nitrogen and twice with syngas. The autoclave was then pressurized to 310 psi with syngas and heated to 95 °C. Gas-liquid chromatography (GLC) analysis of a reaction mixture aliquot indicated the completion of the reaction after 21 hours. The reaction mixture was then cooled down to 25 °C, vented and purged three times with nitrogen to provide a crude product mixture. The crude product mixture was purified by fractional distillation to generate a mixture of Compounds I and II (1071 g, 81% total yield) IFF-10187-WO-PCT containing 88 mol% Compound I and 12 mol% Compound II based on the total amounts of Compounds I and II.

[0089] Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed.

[0090] In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.

[0091] Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

[0092] It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.

Claims

IFF-10187-WO-PCTCLAIM (S)What is claimed is:

1. A hydroformylation process comprising: contacting Compound IVwherein one of the symbols --- is a single bond and the other is a double bond, with carbon monoxide and hydrogen in a reaction zone in the presence of a cobalt catalyst to form a product mixture comprising 2- (octahydro- 1 H-4, 7- methanoinden-5- yl)acetaldehyde (Compound I), wherein the cobalt catalyst is (i) dicobalt octacarbonyl or (ii) a mixture of dicobalt octacarbonyl and a cobalt compound selected from the group of cobalt(ll) acetyl acet on ate, cobalt(lll) acetylacetonate, cobalt(ll) acetate, cobalt(ll) hydroxide, mixtures of cobalt(ll) chloride and an alkali metal carbonate, and combinations thereof.

2. The process of claim 1 , wherein the product mixture further comprises 6- methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde (Compound II).

3. The process of claim 1 or 2, wherein the product mixture further comprises 5- methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde (Compound III).

4. The process of any one of the preceding claims, wherein the cobalt catalyst is a mixture of dicobalt octacarbonyl and a cobalt compound selected from the group of cobalt(ll) acetylacetonate, cobalt(lll) acetylacetonate, cobalt(ll) acetate, cobalt(ll) hydroxide, mixtures of cobalt(ll) chloride and an alkali metal carbonate, and combinations thereof.

5. The process of claim 4, wherein the cobalt compound is selected from the group of cobalt(ll) acetylacetonate, cobalt(lll) acetylacetonate, cobalt(ll) acetate, and combinations thereof.IFF-10187-WO-PCT6. The process of claim 4 or 5, wherein the amount of dicobalt octacarbonyl fed into the reaction zone is no more than 0.1 mol% based on the amount of Compound IV fed into the reaction zone.

7. The process of any one of claims 4-6, wherein the mole ratio of dicobalt octacarbonyl to the cobalt compound is in a range of from 1 :1 to 1 :100.

8. A hydroformylation process comprising:(a) contacting Compound IVwherein one of the symbols --- is a single bond and the other is a double bond, with carbon monoxide and hydrogen in a reaction zone in the presence of a heterogeneous rhodium catalyst to form a product mixture comprising 2-(octahydro- 1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I), wherein the heterogeneous rhodium catalyst comprises carbonyl(hydro)tris[tris(3- sulfophenyl)phosphine]rhodium nonasodium salt.

9. The process of claim 8, wherein the product mixture further comprises 6- methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde (Compound II).

10. The process of claim 8 or 9, further comprising:(b) recovering the rhodium catalyst from the product mixture; and(c) reusing the recovered rhodium catalyst in the hydroformylation step (a).

11. A hydroformylation process comprising: contacting Compound IVIFF-10187-WO-PCTwherein one of the symbols --- is a single bond and the other is a double bond, with carbon monoxide and hydrogen in a reaction zone in the presence of a homogeneous rhodium catalyst to form a product mixture comprising Compound I, wherein the homogeneous rhodium catalyst comprises triphenyl phosphite as ligand.

12. The process of claim 11 , wherein the amount of the homogeneous rhodium catalyst present in the reaction zone is in a range of from about 0.001 mol% to about 0.01 mol% based on the amount of Compound IV fed into the reaction zone.

13. A compound of structural formula (III) in the form of any one of its stereoisomers or a mixture thereof.

14. A mixture of 2-(octahydro-1 H-4,7-methanoinden-5-yl)acetaldehyde (Compound I), 6-methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde (Compound II) and 5- methyloctahydro-1 H-4,7-methanoindene-5-carbaldehyde (Compound III).

15. A fragrance composition comprising an olfactory acceptable amount of the mixture of claim 14.

16. A consumer product comprising the mixture of claim 14.

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