Process for producing unsaturated aldehydes

Abstract

The present invention relates to the field of organic synthesis, more specifically to a process for preparing a compound of formula (I) from a compound of formula (II). The process for preparing a compound of formula (II) and the compound of formula (II) are also part of the present invention.

Description

[Technical field]

[0001] The present invention relates to the field of organic synthesis, more specifically to a process for preparing a compound of formula (I) starting from a compound of formula (II). The process for preparing a compound of formula (II) and the compound of formula (II) are also part of the present invention.

[0002] 2. Background of the Invention The availability of compounds containing unsaturated aldehydes, such as β,γ-, γ,δ- or δ,ε-unsaturated aldehydes, is highly sought after, as they represent highly desirable scaffolds that can be used as such or as key intermediates useful for the preparation of more complex compounds in various fields such as fragrance, cosmetics, pharmaceutics or agrochemistry. In view of this, numerous methodologies have been developed. However, these methodologies suffer from low selectivity, low yields and / or the need for multiple steps.

[0003] Because of the industrial importance of the products, new processes that offer improved yields and selectivities are constantly being sought.

[0004] Therefore, there is a need to develop straightforward methodologies to access such compounds in high yields and high selectivities.

[0005] The present invention provides a solution to the above problem by treating tetrahydrofuran-2-ol or tetrahydro-2H-pyran-2-ol derivatives obtained via hydroformylation with acid in the presence of a polyol or an α-hydroxycarboxylic acid. To the best of the inventors' knowledge, there have been no reports in the prior art of rearrangements as disclosed in the present invention.

[0006] Summary of the Invention The present invention relates to a novel process which allows the preparation of compounds of formula (I) in high yield and selectivity starting from compounds of formula (II). The process of the present invention represents a new and efficient route to compounds of formula (I), which can be easily converted into the corresponding aldehydes of formula (V).

[0007] Thus, a first subject of the invention is a compound of formula [ka] [wherein one dotted line is a carbon-carbon double bond and the other dotted line is a carbon-carbon single bond; m is 0 or 1; R 1 is C 1-12 represents a hydrocarbon group, said group optionally containing 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; R 2 is a hydrogen atom or R 1 represents a group; or R 1 and R 2 Together, C 5-18 Cycloalkyl or C 5-18 cycloalkenyl groups, each of which optionally has one or more hydroxy groups, C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 1-6 Ester, COOH, C 6-10 Aryl and / or C 6-10 R may be substituted with an aryloxy group; 3 and R 4 are each independently a hydrogen atom or C 1-6 Represents an alkyl group; two R a Together, C 2-20 13. A process for preparing a compound in the form of any one of the stereoisomers or a mixture thereof of a compound of formula (II) [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m have the same meaning as defined in formula (I); R c is a hydrogen atom, C 1-12 a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R c is the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (I); n is 0 or 1, R d is C 1-12 is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II a ) and the oxygen atom of formula (II) or a mixture thereof with an acid and a polyol or an α-hydroxycarboxylic acid.

[0008] A second subject of the invention is compounds of formula [ka] [In the formula, m is 0 or 1; R 1 is C 1-12 represents a hydrocarbon group, said group optionally containing 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; R 2 is a hydrogen atom or R 1 represents a group; or R 1 and R 2 Together, C 5-18 Cycloalkyl or C 5-18 cycloalkenyl groups, each of which optionally has one or more hydroxy groups, C 1-15 Alkyl, C2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 1-6 Ester, COOH, C 6-10 Aryl and / or C 6-10 R may be substituted with an aryloxy group; 3 and R 4 are each independently a hydrogen atom or C 1-6 R represents an alkyl group; c is a hydrogen atom, C 1-12 a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R c is the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (II); n is 0 or 1, R d is C 1-12 is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II a ) and the oxygen atom of formula (II) [ka] [In the formula, m, R 1 , R 2 , R 3 and R 4 has the same meaning as defined in formula (II)], in the presence of a hydroformylation catalyst containing a bidentate phosphorus ligand and, optionally, an alcohol or a polyol,

[0009] A further subject of the invention is a compound of formula [ka] [In the formula, m is 0 or 1; R 1 and R 2 are independent of each other, C 1-12 represents a hydrocarbon group, which may optionally contain 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; or R 1 and R 2 Together, C 5-18 Cycloalkyl or C 5-18 cycloalkenyl groups, each of which optionally has one or more hydroxy groups, C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 1-6 Ester, COOH, C 6-10 Aryl and / or C 6-10 R may be substituted with an aryloxy group; 3 and R 4 are each independently a hydrogen atom or C 1-6 R represents an alkyl group; c is a hydrogen atom, C 1-12 a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R c is the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (II); n is 0 or 1, R d is C 1-12 is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II a) and the oxygen atom of formula (II) ], with the exception of 4-butyl-1-[(5,5-dibutyltetrahydro-2-furanyl)oxy]-2,4-octanediol and 2-[(tetrahydro-5,5-dimethyl-2-furanyl)oxy]ethanol.

[0010] Description of the invention It has now surprisingly been found that compounds of formula (II) provide non-conjugated unsaturated aldehydes in high yield and selectivity in the presence of an acid and a polyol, particularly a diol, triol, tetraol or an α-hydroxycarboxylic acid. The rearrangement is novel and has not been reported before. Moreover, compounds of formula (II) can be readily obtained by hydroformylation of allylic or homoallylic alcohols. The present invention provides a three-step straightforward approach to non-conjugated unsaturated aldehydes.

[0011] Thus, a first subject of the invention is a compound of formula [ka] [wherein one dotted line is a carbon-carbon double bond and the other dotted line is a carbon-carbon single bond; m is 0 or 1; R 1 is C 1-12 represents a hydrocarbon group, said group optionally containing 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; R 2 is a hydrogen atom or R 1 represents a group; or R 1 and R 2 Together, C 5-18 Cycloalkyl or C 5-18 cycloalkenyl groups, each of which optionally has one or more hydroxy groups, C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C1-6 Ester, COOH, C 6-10 Aryl and / or C 6-10 R may be substituted with an aryloxy group; 3 and R 4 are each independently a hydrogen atom or C 1-6 Represents an alkyl group; two R a Together, C 2-20 13. A process for preparing a compound in the form of any one of the stereoisomers or a mixture thereof of a compound of formula (II) [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m have the same meaning as defined in formula (I); R c is a hydrogen atom, C 1-12 a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R c is the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (I); n is 0 or 1, R d is C 1-12 is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II a ) and the oxygen atom of formula (II) or a mixture thereof with an acid and a polyol or an α-hydroxycarboxylic acid.

[0012] For the sake of clarity, expressions such as "any one of the stereoisomers or a mixture thereof" have the usual meaning understood by a person skilled in the art, i.e., the compounds of formula (I) and (II) may be pure enantiomers or a mixture of enantiomers. In other words, the compounds of formula (I) and (II) may have at least one stereocenter that may have two different stereochemistries (e.g., R or S). The compounds of formula (I) and (II) may be in the form of pure enantiomers or even in the form of a mixture of enantiomers. The compounds of formula (I) and (II) may be in the form of pure diastereomers or even in the form of a mixture of diastereomers, if the compounds of formula (I) and (II) have two or more stereoisomers. The compounds of formula (I) and (II) may be in the form of racemic or scalemic form. Thus, the compounds of formula (I) and (II) may be in the form of one stereoisomer or a composition of matter that includes or consists of various stereoisomers.

[0013] For clarity, expressions such as "one dotted line is a carbon-carbon double bond and the other dotted line is a carbon-carbon single bond" have the ordinary meaning as understood by a person skilled in the art, i.e., the entire bond (solid and dotted) between the carbon atoms connected by the dotted line is a carbon-carbon single or double bond. [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , R a and m has the same meaning as defined above]. Those skilled in the art will appreciate that the compound of formula (I''') may be in the form of any one of the stereoisomers or a mixture thereof, 2 It is well recognized that this is only formed when the atom is not a hydrogen atom.

[0014] For the sake of clarity, wavy bonds and the like in compounds (I'), (I'') and (I''') have the usual meaning as understood by the skilled artisan, i.e., it means that the double bond can have a cis configuration corresponding to the Z isomer, a trans configuration corresponding to the E isomer, or a mixture thereof. Indeed, all compounds of the invention having a double bond may be in the form of their E or Z isomer or a mixture thereof. In other words, the compound of formula (I) may be in the form of its E or Z isomer or a mixture thereof, for example, the method of the invention results in a composition of matter consisting of one or more compounds of formula (I) having the same chemical structure but different configurations of the double bonds. In particular, the compound of formula (I) may be in the form of a mixture consisting of isomers E and Z, where said isomer E represents at least 50% or even at least 75% of the total mixture (i.e., mixture E / Z=75 / 25-100 / 0).

[0015] The term "optionally" is understood to mean that the particular group that is optionally substituted may or may not be substituted with the particular functional group. The term "one or more" is understood to mean that the particular group is substituted with 1 to 7, preferably 1 to 5, preferably 1 to 3, and more preferably 1 to 2 functional groups.

[0016] "...hydrocarbon group..." is understood to mean that said group consists of hydrogen and carbon atoms and may be in the form of an aliphatic hydrocarbon, i.e. linear or branched saturated hydrocarbon (e.g. alkyl group), linear or branched unsaturated hydrocarbon (e.g. alkenyl or alkynyl group), saturated cyclic hydrocarbon (e.g. cycloalkyl) or unsaturated cyclic hydrocarbon (e.g. cycloalkenyl or cycloalkynyl group), aromatic hydrocarbon, i.e. aryl group, or mixtures of said types of groups, e.g. a particular group may contain linear alkyl, branched alkenyl (e.g. having one or more carbon-carbon double bonds), (poly)cycloalkyl and aryl moieties, unless a specific limitation to only one type is mentioned. Similarly, in all embodiments of the present invention, when a group is referred to as being in the form of more than one type of topology (e.g., linear, cyclic or branched) and / or being saturated or unsaturated (e.g., alkyl, aromatic or alkenyl), it also means the group can have any one of said topologies or contain moieties that are saturated or unsaturated, as explained above. Similarly, in all embodiments of the present invention, when a group is referred to as being in the form of one type of saturated or unsaturated (e.g., alkyl), it means that the group can be in any type of topology (e.g., linear, cyclic or branched) or have several moieties with various topologies.

[0017] The term "hydrocarbon group...said group optionally comprises" is understood to mean that said hydrocarbon group optionally comprises one, two or three oxygen atoms in the form of an alcohol, ketone, aldehyde, ether, ester, carboxylic acid, carbonate group, and / or one or two nitrogen atoms in the form of an amine or amide group, and / or one sulfur atom in the form of a thiol group. These groups may be attached laterally to said hydrocarbon, replacing a hydrogen atom of the hydrocarbon group, or may be incorporated into the hydrocarbon chain (where chemically possible), replacing a carbon atom of the hydrocarbon group. For example, the -CH2-CH2-CHOH-CH2- group represents a C4 hydrocarbon group containing an alcohol group (substitution of a hydrogen atom), i.e., a C4 hydrocarbon containing an oxygen atom, the -CH2-CH2-COO-CH2-CH2CH2-CH2- group represents a C7 hydrocarbon group containing one ester group (substitution of a carbon atom / incorporation into the hydrocarbon chain), i.e., a C7 hydrocarbon containing two oxygen atoms, and similarly, the -CH2-CH2-O-CH2-CH2-O-CH2-CH2- group represents a C6 hydrocarbon group containing two ether groups, i.e., a C6 hydrocarbon containing two oxygen atoms. 1 or R 2 It is understood that the first atom of a group is always a carbon atom.

[0018] The terms "alkyl", "alkenyl" and "alkoxy" are understood to include branched and straight chain alkyl and alkenyl groups. The terms "alkenyl" and "cycloalkenyl" are understood to include one, two or three olefinic double bonds, preferably one or two olefinic double bonds. The terms "cycloalkyl" and "cycloalkenyl" are understood to include monocyclic or fused, spiro and / or bridged bicyclic or tricyclic cycloalkyl and cycloalkenyl groups, preferably monocyclic cycloalkyl and cycloalkenyl groups.

[0019] The term "aryl" is understood to include any group that contains at least one aromatic group, such as a phenyl, indenyl, indanyl, tetrahydronaphthalenyl or naphthalenyl group.

[0020] To be clear, "R 1 and R 2 Together, C 3-18 Cycloalkyl or C 5-18 The phrase "form a cycloalkenyl group" means that the carbon atom to which the two groups are attached is C 5-18 Cycloalkyl or C 5-18 It is meant to be included in the cycloalkenyl group.

[0021] The term "alkanediyl" is understood to include branched, straight-chain, cyclic and alicyclic alkanediyl groups.

[0022] The term "oxo group" is understood to include any group of formula =O, i.e., ketones or aldehydes, etc. In other words, C optionally substituted with an oxo group. 1-7 An alkyl group is an alkyl group having from 1 to 7 carbons, one of which may be a terminal carbon or may be substituted with one =O group in place of two hydrogen atoms.

[0023] The term "hydrocarbylene group" is understood as a divalent group formed by removing two hydrogen atoms from a hydrocarbon group.

[0024] For clarity, terms such as "polyol" have their ordinary meaning as understood by those skilled in the art, i.e., a compound having at least two hydroxy groups. Polyols can contain additional functional groups such as ether, ester or acid groups.

[0025] To be clear, R c Formula (II a ) the compound of formula (II) has the formula [ka] [In the formula, R 1 , R 2 , R 3 、 R 4 , R d , n and m have the same meanings as defined above] or in the form of any one of the stereoisomers or a mixture thereof.

[0026] According to any embodiment of the invention, compound (I) may be in the form of a mixture of compounds of formula (I'), (I'') and (I'''), said compounds of formula (I') representing at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or even at least 90% of the total mixture. In particular, the compound of formula (I) is a compound of formula (I').

[0027] According to any embodiment of the invention, when the compound of formula (I) is in the form of a mixture of compounds of formula (I'), (I'') and (I'''), the process of the invention can further comprise an isomerization step, thereby obtaining mainly one isomer or increasing the amount of one isomer. The skilled person is familiar with the conditions suitable for isomerization, for example under acidic conditions or in the presence of a metal catalyst, either in free or supported form or as a rhodium, ruthenium, iridium, platinum or palladium complex.

[0028] According to any embodiment of the present invention, when m is 0, the compounds of formula (I), (I'), (I'') and (I''') are each represented by the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and R ahas the same meaning as defined above] or in the form of any one of the stereoisomers or a mixture thereof.

[0029] According to any embodiment of the present invention, R 3 is a hydrogen atom or C 1-4 In particular, R 3 is a hydrogen atom or C 1-3 In particular, R 3 may be a hydrogen atom or a methyl or ethyl group. Even more specifically, R 3 may be a hydrogen atom or a methyl group.

[0030] According to any embodiment of the present invention, m is 0.

[0031] According to any embodiment of the present invention, R 4 is a hydrogen atom or C 1-4 In particular, R 4 is a hydrogen atom or C 1-3 In particular, R 4 may be a hydrogen atom or a methyl or ethyl group. Even more specifically, R 4 may be a hydrogen atom.

[0032] According to any embodiment of the present invention, R c is a hydrogen atom, C 2-10 a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R c is represented by the above-defined formula (II a In particular, R c is a hydrogen atom, C 2-10 may be a hydrocarbon group, which may be optionally substituted with one oxo group or one or three hydroxy groups, and may optionally contain one or two ether functions, or R c is represented by the above-defined formula (II a In particular, R c is a hydrogen atom, C1-8 an alkyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups, or R c is represented by the above-defined formula (II a In particular, R c is a hydrogen atom, C 1-7 an alkyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups, or R c is represented by the above-defined formula (II a In particular, R c is a hydrogen atom, C 1-6 an alkyl group, which may be optionally substituted with one or two hydroxy groups, or R c is represented by the above-defined formula (II a In particular, R c is a hydrogen atom, C 1-4 an alkyl group, which may be optionally substituted with one or two hydroxy groups, or R c is represented by the above-defined formula (II a ) where n is 1. In particular, R c is a hydrogen atom, C 1-3 an alkyl group, which may be optionally substituted with one or two hydroxy groups, or R c is represented by the above-defined formula (II a ) where n is 1. In particular, R c is C 1-3 It may be an alkyl group, which may be optionally substituted with one hydroxy group. Even more specifically, R c is (CH2) n It may be an OH group, where n is 2 or 3 or 4, in particular n is 2.

[0033] According to any embodiment of the present invention, R d is C 2-10It may be a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms. In particular, R d is C 2-10 It may be a hydrocarbylene group, which may be optionally substituted with one oxo group or one or three hydroxy groups, and may optionally contain one or two ether functional groups. In particular, R d is C 2-8 It may be an alkanediyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups. In particular, R d is C 2-7 It may be an alkanediyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups. In particular, R d is C 2-6 It may be an alkanediyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups. In particular, R d is C 2-6 It may be an alkanediyl group, which may be optionally substituted with one oxo or hydroxy group. In particular, R d is C 2-4 It may be an alkanediyl group, which may be optionally substituted with an oxo group or a hydroxy group. d is C 2-3 It may be an alkanediyl group, which may be optionally substituted with one hydroxy group. In particular, R d is C 2-3 It may be an alkanediyl group, which may be optionally substituted with one hydroxy group. Even more specifically, R d is (CH2) n group, where n is 2 or 3 or 4, in particular n is 2.

[0034] According to any embodiment of the present invention, R 1 and R 2 The total number of carbon atoms in the group is at least five.

[0035] According to any embodiment of the present invention, R 2 is a hydrogen atom or C 1-10 It may be a hydrocarbon group, which may optionally contain 1 to 3 oxygen atoms. In particular, R 2 is a hydrogen atom or C 1-10 It may be an alkyl group, which may optionally contain one or two oxygen atoms. In particular, R 2 is a hydrogen atom or C 1-8 In particular, R 2 is a hydrogen atom or C 1-6 In particular, R 2 is a hydrogen atom or C 1-4 In particular, R 2 is a hydrogen atom or C 1-3 In particular, R 2 may be a hydrogen atom or a methyl or ethyl group. Even more specifically, R 2 may be a hydrogen atom or a methyl group.

[0036] According to any embodiment of the present invention, R 1 is C 1-10 It may be a hydrocarbon group, which may optionally contain 1 to 3 oxygen atoms. In particular, R 1 is C 1-10 It may be an alkyl group, which may optionally contain 1 to 2 oxygen atoms, or it may be a phenyl group or a benzyl group, which may optionally contain 1 to 3 C 1-3 Alkoxy group, C 1-6 Alkyl group or C 2-6 In particular, R 1 is C 1-8 It may be an alkyl group, which may optionally contain 1 to 2 oxygen atoms, or a phenyl or benzyl group, which may optionally contain 1 to 2 methoxy or ethoxy groups or C 1-4 In particular, R 1 is C 1-6may be an alkyl group, a phenyl group or a benzyl group, said group being optionally 1-3 Optionally, R is substituted with an alkyl group. 1 may be a phenyl or benzyl group, which may be optionally substituted with a methyl or ethyl group.

[0037] According to any embodiment of the present invention, R 1 and R 2 Together, C 5-16 Cycloalkyl or C 5-16 Cycloalkenyl groups can be formed, each of which optionally contains one or more hydroxy, C 1-12 Alkyl, C 2-12 Alkenyl, C 1-12 Alkoxy, C 3-12 Cycloalkyl, C 5-12 Cycloalkenyl, C 1-6 Ester, COOH, C 6-10 Aryl and / or C 6-10 In particular, R 1 and R 2 Together, C 5-14 Cycloalkyl or C 5-14 cycloalkenyl groups, each of which optionally has one or more C 1-12 Alkyl, C 1-12 Alkoxy, C 3-12 Cycloalkyl, C 6-10 Aryl and / or C 6-10 In particular, R 1 and R 2 Together, C 5-12 Cycloalkyl or C 5-12 cycloalkenyl groups, each of which optionally contains one or two C 1-10 In particular, R 1 and R 2 Together, C 5-10 Cycloalkyl or C 5-10 cycloalkenyl groups, each of which optionally contains one or two C1-10 In particular, R 1 and R 2 Together, C 5-8 Cycloalkyl or C 5-8 cycloalkenyl groups, each of which optionally contains one or two C 1-10 In particular, R 1 and R 2 Together, C 5-6 Cycloalkyl or C 5-6 cycloalkenyl groups, each of which optionally contains one or two C 1-8 In particular, R 1 and R 2 Together, C 5-6 Cycloalkyl or C 5-6 cycloalkenyl groups, each of which optionally contains one or two C 1-6 In particular, R 1 and R 2 Together, C 5-6 Cycloalkyl or C 5-6 cycloalkenyl groups, each of which optionally contains one or two C 1-4 In particular, R 1 and R 2 Together, C 5-6 or C 5-6 It forms cycloalkenylcycloalkyl groups, each of which is optionally substituted with one or two methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, or tert-butyl groups.

[0038] According to any embodiment of the present invention, the compound of formula (I) has the formula [ka] [In the formula, each R a has the same meaning as defined above, and R 5 and R 6 are each independently a hydrogen atom, C1-6 represents an alkyl group], and the compound of formula (II) is in the form of any one of the stereoisomers or a mixture thereof, [ka] [In the formula, each R 5 and R 6 has the same meaning as defined above], or in the form of any one of the stereoisomers or mixtures thereof.

[0039] According to any embodiment of the present invention, R 6 is a hydrogen atom or C 1-4 In particular, R 6 is a hydrogen atom or C 1-3 In particular, R 6 may be a hydrogen atom or a methyl or ethyl group. Even more specifically, R 6 may be a methyl group.

[0040] According to any embodiment of the present invention, R 5 is a hydrogen atom or C 1-4 In particular, R 5 is a hydrogen atom or C 1-3 In particular, R 5 may be a hydrogen atom or a methyl or ethyl group. Even more specifically, R 5 may be a methyl group.

[0041] According to any embodiment of the present invention, the acid is a Lewis acid or a Bronsted acid. The acid has a pH of less than 3. Non-limiting examples of acids suitable for the method of the present invention include pTsOH, MsOH, TfOH, H2SO4, HCl, H3PO4, KHSO4, NaHSO4, BF3·Et2O, BF3·(AcOH)2, ZnBr2, Fe(OTf)3, Fe(OTs)3, FeCl3, Zn(OTf)2, Bi(OTf)3, Cu(OTf)2, Al(OTf)3, SnCl4, Alox acidic (Axsorb A2-5, Al2O3504C), Amberlyst 15, Amberlyst 35, SiO2, Wayphos, polyphosphoric acid, zeolites (CBV 21A available from Zeolyst, CBV 22 available from Zeolyst, etc.), and / or tetrahydrofuran (Trifluoroethylene, tetrafluoroethylene, etc.). 780, CP814E sold by Zeolyst, Boric Acid, CSA, K10-S300 (Bentonite) sold by Clariant, F24 X (Clay) sold by EP minerals, F21 X (Clay) sold by EP minerals, Siral® 40 HPV sold by Sasol.

[0042] The acid can be added to the reaction medium of the process of the invention in a wide range of concentrations. As non-limiting examples, values ​​of acid concentration can be mentioned in the range of about 1 to about 100 mol% relative to the amount of the compound of formula (II), preferably 1 to about 50 mol% relative to the amount of the compound of formula (II), preferably 1.5 to about 2.5 mol% relative to the amount of the compound of formula (II). As the skilled person knows, the optimum concentration of the acid depends on the nature of the acid, the nature of the compound of formula (II), the reaction temperature and the desired reaction time.

[0043] According to any embodiment of the present invention, the polyol used in the process for preparing the compound of formula (I) is a diol, triol, tetraol or pentaol. In particular, the polyol has the formula HOROH, where R is C 2-12 R is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, in particular R is C 2-10R is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, in particular R is C 2-10 R is a hydrocarbylene group, which may optionally be substituted with one oxo group or one to three hydroxy groups and may optionally contain one or two ether functions, in particular R is 2-8 R is an alkanediyl group, which may be optionally substituted with one or two hydroxy groups and may optionally contain an ether function, in particular R is 2-6 R may be an alkanediyl group, which may be optionally substituted with one or two hydroxy groups, in particular R is 2-4 R may be an alkanediyl group, which may be optionally substituted with a hydroxy group, in particular R may be a linear C 2-4 R may be an alkanediyl group, which may be optionally substituted with a hydroxy group, in particular R may be a linear C 2-3R may be an alkanediyl group, which may be optionally substituted with a hydroxy group, and even more particularly R may be a 1,2-ethanediyl group. In particular, the polyol is a diol, in particular a 1,2-alkanediol, a 1,3-alkanediol or a 1,4-alkanediol. Non-limiting examples of diols suitable for the method of the present invention include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-2,3-diol, 1,2-butanediol, 1,2-pentanediol, 2,3-dimethyl-3-hydroxy-2-butanol, glycerol, diglycerol, triglycerol, erythritol, threitol, trans-1,2-cyclohexanediol, cis-1,2-cyclohexanol, 1,2-cyclopentanol, neopentyl glycol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,2-propanediol, 2,2-dimethyl-1,3-propanediol, The diol may be selected from the group consisting of pentane-2,4-diol, 2-methylpentane-2,4-diol, butane-1,3-diol, 3-methylbutane-1,3-diol, 2-methylpropane-1,3-diol, 2-methylpropane-1,2,3-triol, 1,3-dihydroxypropan-2-one, 1,4-butanediol, hexane-2,5-diol, 2,5-dimethylhexane-2,5-diol, 2-methylhexane-2,5-diol, 2,2-dimethylbutane-1,4-diol, 1,2-benzenedimethanol, 2-hydroxybenzyl alcohol, (Z)-but-2-ene-1,4-diol, pentaerythritol. In particular, the diol may be selected from the group consisting of ethylene glycol, 2,2-dimethylpropane-1,3-diol and propane-1,3-diol.

[0044] The polyols, such as diols, triols or tetraols, can be added to the reaction medium of the process of the present invention in a wide range of concentrations. As non-limiting examples, values ​​in the range of about 1 to about 12 equivalents relative to the amount of the compound of formula (II), preferably 2 to about 12 equivalents relative to the amount of the compound of formula (II), preferably 3 to about 5 equivalents relative to the amount of the compound of formula (II) can be cited as diol or triol concentration values. As the skilled person knows, the optimum concentration of the diol or triol depends on the nature of the diol or triol, the nature of the compound of formula (II), the reaction temperature and the desired reaction time.

[0045] According to any embodiment of the present invention, the α-hydroxycarboxylic acid has the formula R′CH(OH)COOH, where R′ is a hydrogen atom or 1-6 is an alkyl group, in particular R' is a hydrogen atom or 1-4 In particular, R′ is a hydrogen atom or a C 1-3 In particular, R′ is a hydrogen atom or a C 1-2 R' may be an alkyl group, and even more specifically, R' may be a hydrogen atom or a methyl group. Non-limiting examples of α-hydroxycarboxylic acids suitable for the method of the present invention may be selected from the group consisting of lactic acid and glycolic acid.

[0046] The α-hydroxycarboxylic acid can be added to the reaction medium of the process of the present invention in a wide range of concentrations. As non-limiting examples, values ​​of the α-hydroxycarboxylic acid concentration can be mentioned in the range of about 2 to about 12 equivalents relative to the amount of the compound of formula (II), preferably 3 to about 5 equivalents relative to the amount of the compound of formula (II). As the skilled person knows, the optimum concentration of the α-hydroxycarboxylic acid depends on the nature of the α-hydroxycarboxylic acid, the nature of the compound of formula (II), the reaction temperature and the desired reaction time.

[0047] According to any embodiment of the present invention, two R a Together, C 2-18represents a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms. In particular, two R a Together, C 2-16 represents a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms. In particular, two R a Together, C 2-14 represents a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms. In particular, two R a Together, C 2-12 represents a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms. In particular, two R a Together, C 2-10 represents a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms. In particular, two R a Together, C 2-10 represents a hydrocarbylene group, which may optionally be substituted with one oxo group or one or three hydroxy groups and may optionally contain one or two ether functions, in particular two R a Together, C 2-8 represents an alkanediyl group, which may be optionally substituted with an oxo group or one or two hydroxy groups. a Together, C 2-8 represents an alkanediyl group, which may be optionally substituted with an oxo group or a hydroxy group. a Together, C 2-6 It may represent an alkanediyl group, which may be optionally substituted with an oxo group or a hydroxy group. In particular, two R a Together, C 2-4 It may represent an alkanediyl group, which may be optionally substituted with an oxo group or a hydroxy group. In particular, two R a Together, C 2-3 It may represent an alkanediyl group, which may be optionally substituted with an oxo group or a hydroxy group. Even more specifically, R atogether can represent a 1,2-ethanediyl group, a 1,3-propanediyl group or a 2,2-dimethylpropane-1,3-diyl group.

[0048] According to a particular embodiment of the invention, when the polyol is a tetraol, the compound of formula (I) has the formula [ka] [Wherein, dotted line, R 1 , R 2 , R 3 , R 4 and m have the same meaning as defined in formula (I); R a ' is C 2-8 Alkanetetrayl groups, in particular R a ' is C 3-6 It may be in the form of a dimer of the formula:

[0049] According to a particular embodiment of the invention, the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (I)] may be formed during the process of the invention in the form of any one of the stereoisomers or a mixture thereof. The compound of formula (VIII) is converted to the compound of formula (II) in the process of the invention.

[0050] According to any one of the embodiments of the present invention, the method for preparing the compound of formula (I) of the present invention is carried out at a temperature of 20°C to 250°C. In particular, the temperature is in the range of 90°C to 145°C. Of course, the person skilled in the art can also select the preferred temperature according to the melting and boiling points of the starting and final products and the desired reaction time or conversion rate.

[0051] The process for preparing the compounds of formula (I) of the present invention can be carried out in the presence or absence of a solvent. If a solvent is required or used for practical reasons, any solvent currently used in such reaction types can be used for the purposes of the present invention. Non-limiting examples include C benzene, such as toluene, xylene, 1,3-diisopropylbenzene, cumene, chlorobenzene or pseudocumene. 6-12 Examples include aromatic solvents or mixtures thereof, hydrocarbon solvents such as cyclohexane or heptane, octane, or ether solvents such as methyltetrahydrofuran. The choice of solvent depends on the nature of the substrate and / or catalyst, and the skilled person is fully capable of choosing the most suitable solvent in each case to optimize the reaction.

[0052] According to any one of the embodiments of the present invention, the water produced during the process of the present invention is continuously removed during the process of the present invention. The removal of the water formed during the process of the present invention can be carried out by distillation, azeotropic distillation, addition of a drying agent or an orthoformate.

[0053] Non-limiting examples of suitable compounds of formula (I) include 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane, 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane, 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4-propyl-1,3-dioxolane, 2 -(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4,5-dimethyl-1,3-dioxolane, 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane, 3,9-bis(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-2,4,8,10-tetraoxaspiro[5.5]Undecane, 2-(3-(4,4-dimethylcyclohex-1-en-1-yl)propyl)-1,3-dioxolane, (E)-2-(3,7-dimethyloct-3-en-1-yl)-1,3-dioxolane / (Z)-2-(3,7-dimethyloct-3-en-1-yl)-1,3-dioxolane / (E)-2-(3,7-dimethyloct-2-en-1-yl)-1,3-dioxolane / (Z)-2-(3,7-dimethyloct-2-en-1-yl)-1,3-dioxolane / 2 -(7-Methyl-3-methyleneoctyl)-1,3-dioxolane, 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxan-5-ol, (2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolan-4-yl)methanol, 2-(2-(4-(tert-butyl)cyclohex-1-en-1-yl)ethyl)-1,3-dioxolane, 2-(2-(5-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane 2-(2-(3-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane, 2-(2-(4-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane, 2-(2-(4-butylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane, 2-(2-(4-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane, 2-(2-(3-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)ethyl)-1,3-dioxolane, (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane, (Z)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane, (E / Z)-2-(3-methyl-4-(p-tolyl)but-2-en-1-yl)-1,3-dioxolane, 2-(3-(4-methylbenzyl)but-3-en-1-yl)-1,3-dioxolane. Non-limiting examples of suitable compounds of formula (II) include 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol, 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-1-ol, 1-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-2-ol, 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butan-2-ol, 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)-2,2-dimethylpropan-1-ol, 2-(((8,8 -Dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)methyl)-2-(hydroxymethyl)propane-1,3-diol, 2-((9,9-dimethyl-1-oxaspiro[5.5]undecan-2-yl)oxy)ethan-1-ol, 2-((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol, 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)methyl)-2-(hydroxymethyl)propane-1,3-diol, 2-((8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)propane-1,2-diol, 2-((8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol, 2-((7-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol, 2-((8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol, 2-((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol, Examples of the 2-((pyro[4.5]decan-2-yl)oxy)ethan-1-ol include 2-((7-isopropyl-1-oxaspiro[4.4]nonan-2-yl)oxy)ethan-1-ol, 2-((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol, and 2-((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethan-1-ol.

[0054] According to any embodiment of the present invention, the process for preparing the compounds of formula (I) of the present invention may be carried out under batch conditions and / or under continuous conditions.

[0055] According to any embodiment of the present invention, the compound of formula (I) has the formula [ka] [Wherein, dotted line, m, R 1 , R 2 , R 3 and R 4 has the same meaning as defined above] or a compound in the form of a mixture thereof. The conversion of the compound of formula (I) to the compound of formula (V) is a deprotection that is mostly reported in the prior art. According to any embodiment of the present invention, the deprotection of the acetal group to obtain the compound of formula (V) can be carried out under conventional conditions known to those skilled in the art, i.e., in water with a large molar excess of a carboxylic acid. Specific and non-limiting examples of carboxylic acids can be selected from the group consisting of acetic acid, propionic acid, citric acid, formic acid, TFA, oxalic acid or mixtures thereof. Optionally, the deprotection can be carried out in a C 2 -based solvent such as ethylene glycol, or methanol, ethanol or propanol. 1-6 It can be carried out in the presence of an alcohol or in the presence of a strong acid.

[0056] The carboxylic acid used for deprotection can be added to the reaction medium of the method of the present invention in a wide range of concentrations. As a non-limiting example, values ​​of acid concentration in the range of about 5 to about 20 equivalents relative to the substrate mass, preferably 5 to about 10 equivalents relative to the substrate mass, can be mentioned. As known to those skilled in the art, the optimal concentration of acid depends on the nature of the acid, the nature of the substrate, the reaction temperature and the desired reaction time.

[0057] Ethylene glycol or C used for deprotection 1-6 The alcohol can be added to the reaction medium of the process of the present invention in a wide range of concentrations. As a non-limiting example, values ​​ranging from about 5 to about 20 equivalents relative to the substrate weight, preferably from 5 to about 10 equivalents relative to the substrate weight, are used for ethylene glycol or C 1-6The concentration of the strong acid may be exemplified as a concentration value of the alcohol. As known to those skilled in the art, the optimum concentration of the acid depends on the nature of the acid, the nature of the substrate, the reaction temperature and the desired reaction time. The strong acid may be added to the reaction medium of the method of the present invention in a wide range of concentrations. As a non-limiting example, the acid concentration may be exemplified as a value ranging from about 1 mol% to about 50 mol% equivalent to the substrate mass, preferably from 5 to about 10 mol% to the substrate mass.

[0058] According to any one of the embodiments of the present invention, the formation of the compound of formula (V) by deprotection can be carried out at a temperature of 40° C. to 120° C. In particular, the temperature ranges from 70° C. to 90° C. Of course, the skilled person can also select the preferred temperature depending on the melting and boiling points of the starting and final products and the desired reaction time or conversion rate.

[0059] According to any one of the embodiments of the present invention, the formation of the compound of formula (V) by deprotection can be carried out in the presence or absence of a solvent. If a solvent is required or used for practical reasons, any solvent currently used in such reaction types can be used for the purposes of the present invention. As non-limiting examples, C toluene, xylene, 1,3-diisopropylbenzene, cumene or pseudocumene or mixtures thereof can be used. 6-12 Examples of suitable solvents include aromatic solvents, alcoholic solvents such as methanol, ethanol, 2-methylbutan-2-ol or mixtures thereof, hydrocarbon solvents such as cyclohexane, heptane or mixtures thereof, ester solvents such as n-butyl acetate, isopropyl acetate, ethyl acetate, or ether solvents such as methyltetrahydrofuran, tetrahydrofuran or mixtures thereof. The choice of solvent depends on the nature of the substrate and the carboxylic acid derivative, and the skilled person is fully capable of choosing the most convenient solvent in each case to optimize the reaction.

[0060] According to any embodiment of the invention, the compound of formula (II) can be prepared by hydroformylation. Thus, another subject of the invention is a compound of formula [ka] [In the formula, m is 0 or 1; R 1 is C 1-12 represents a hydrocarbon group, said group optionally containing 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; R 2 is a hydrogen atom or R 1 represents a group; or R 1 and R 2 Together, C 5-18 Cycloalkyl or C 5-18 cycloalkenyl groups, each of which optionally has one or more hydroxy groups, C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 1-6 Ester, COOH, C 6-10 Aryl and / or C 6-10 R may be substituted with an aryloxy group; 3 and R 4 are each independently a hydrogen atom or C 1-6 R represents an alkyl group; c is a hydrogen atom, C 1-12 a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R c is the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (II); n is 0 or 1, R d is C 1-12 is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II a) and the oxygen atom of formula (II), [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (II)] or a mixture thereof, in the presence of a hydroformylation catalyst comprising a bidentate phosphorus ligand and optionally an alcohol or a polyol.

[0061] For clarity, expressions such as "hydroformylation" have their ordinary meaning as understood by those skilled in the art, i.e., the reaction is carried out in the presence of a metal catalyst, such as a rhodium, cobalt or platinum complex, preferably a rhodium complex, carbon monoxide, hydrogen and a bidentate phosphorus ligand.

[0062] According to any embodiment of the present invention, the polyol used in the preparation of the compound of formula (II), i.e. in the hydroformylation, is a C 1-10 In particular, the polyol may be a C 1-10 It may be a hydrocarbon. In particular, the polyol may be a diol or triol having 1 to 8 carbon atoms. In particular, the polyol may be a diol.

[0063] According to any embodiment of the present invention, the hydroformylation of a compound of formula (VI) may be carried out in the presence of an alcohol or a polyol.

[0064] According to any embodiment of the present invention, the diol has the formula HOR d OH [wherein, R d is C 2-10A hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms; in particular, R d is a hydrogen atom, C 2-10 may be a hydrocarbylene group, which may be optionally substituted with one oxo group or one or three hydroxy groups and may optionally contain one or two ether functions; in particular R d is C 2-8 alkanediyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups; in particular R d is C 2-7 alkanediyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups; in particular R d is C 2-6 an alkanediyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups; R d is C 2-6 an alkanediyl group, which may be optionally substituted with one oxo or hydroxy group, in particular R d is C 2-4 In particular, R d is a linear C 2-4 and more specifically, R d may be a 1,2-ethanediyl group. Non-limiting examples of diols suitable for the process of the present invention may be selected from the group consisting of ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-2,3-diol.

[0065] According to any embodiment of the present invention, the alcohol has the formula R e OH [wherein, R e is C 1-6 Alkyl groups, particularly R e is C 1-4 It may be an alkyl group, in particular R e is C 1-3 It may be an alkyl group, in particular R eis C 1-2 and more specifically, R e may be a methyl group. Non-limiting examples of alcohols suitable for the process of the present invention may be selected from the group consisting of methanol, ethanol, propanol and butanol.

[0066] The diol or alcohol can be added to the reaction medium of the process of the invention in a wide range of concentrations. As non-limiting examples, values ​​in the range of about 1 to about 12 equivalents relative to the amount of the compound of formula (VI), preferably about 3.4 to about 12 equivalents relative to the amount of the compound of formula (VI), preferably about 3.5 to about 5 equivalents relative to the amount of the compound of formula (VI) can be mentioned as diol or alcohol concentration values. In particular, the alcohol or diol is added to the reaction medium in a concentration of at least 3.4 equivalents relative to the amount of the compound of formula (VI). As the skilled person knows, the optimum concentration of the diol depends on the nature of the diol, the nature of the compound of formula (VI), the reaction temperature, the crystallization behavior of the reaction product, and the desired reaction time.

[0067] According to any embodiment of the present invention, the hydroformylation is carried out in the presence of a rhodium complex. Rhodium complexes that can be used in the present invention include, but are not limited to, Rh(acac)(CO)2, RhCl3, Rh2AcO4, [Rh(OAc)(COD)]2, Rh4(CO) 12 , Rh6(CO) 16, RhCl(CO)(PPh3)2, Rh(C2H4)2(acac), [Rh(Cl)(COD)]2, [Rh(Cl)(COE)2]2, [Rh(OAc)(CO)2]2, Rh(acac)(COD), HRh(CO)(PPh3)3, RhCl(PPh3)3, [Rh(NBD)2]BF4, [Rh(OMe)(COD)]2 and [Rh(OH)(COD)]2, where acac represents an acetylacetonate group, Ac represents an acetyl group, COD represents a 1,5-cyclooctadiene group, COE represents a cyclooctene group, and Ph represents a phenyl group. In particular, the rhodium complex may be selected from the group consisting of Rh(acac)(CO)2, [Rh(OAc)(COD)]2, RhCl(CO)(PPh3)2, Rh(C2H4)2(acac), [Rh(Cl)(COD)]2, [Rh(Cl)(COE)2]2, [Rh(OAc)(CO)2]2, Rh(acac)(COD), HRh(CO)(PPh3)3, RhCl(PPh3)3, [Rh(NBD)2]BF4, [Rh(OMe)(COD)]2 and [Rh(OH)(COD)]2. Even more particularly, the rhodium complex may be selected from the group consisting of Rh(acac)(CO)2, Rh(acac)(COD), HRh(CO)(PPh3)3, [Rh(OMe)(COD)]2 and [Rh(OH)(COD)]2. The complexes can be added to the reaction medium of the method of the invention in a wide range of concentrations. Non-limiting examples of complex concentration values ​​include values ​​ranging from about 0.0005 mol% to about 5 mol% relative to the substrate mass, preferably from about 0.001 mol% to about 5 mol% relative to the substrate mass. Preferably, the complex concentration is 0.0025 mol% to 2 mol%. It goes without saying that the optimum concentration of the complex depends on the nature of the complex, the nature of the substrate, the nature of the ligand, the reaction temperature and the desired reaction time, as known to those skilled in the art.

[0068] According to any embodiment of the present invention, the hydroformylation is carried out in the presence of a bidentate phosphorus ligand.

[0069] According to any one of the above embodiments, the hydroformylation is carried out using the bidentate phosphorus ligand 3,9-bis[2,4-bis(1-methyl-1-phenyl-ethyl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane or a compound of formula [ka] [In the formula, each R 9 are each independently a C4 heteroaryl group, an optionally substituted C 6-10 represents an aromatic group, or an optionally substituted cyclohexyl group, or two R 9 taken together represent 1,1'-biphenyl-2,2'-dioxy, 1,1'-biphenyl-2,2'-dimethyl, or 1,1'-biphenyl]-2,2'-diyl, each of which is optionally substituted; Q is the formula - a) [ka] [wherein q is 0 or 1, each T independently represents an oxygen atom or a CH2 group, and each R 10 are each independently a hydrogen atom or C 1-8 represents an alkyl group, Z is an oxygen atom, a sulfur atom, or a C(R 11 )2, Si(R 12 )2 or NR 11 represents a group, R 11 is a hydrogen atom or R 12 is a group, R 12 is C 1-4 represents a linear or branched alkyl group, preferably a methyl group, or - b) [ka] [wherein q is 0 or 1, r is 0 or 1, each T independently represents an oxygen atom or a CH2 group, and R 13 are each independently a hydrogen atom, a methoxy group or C 1-4alkyl, which is optionally substituted with 1 to 3 halogen atoms or alkoxy groups; or two adjacent R 13 together can represent a (CH)4 group, - c) [ka] [Wherein, T, q and R 13 represents the enantiomeric form of any one of the groups Q, Q having the same meaning as above and the wavy line indicating the position of the bond between said Q group and the remainder of compound (A).

[0070] According to any one of the above embodiments, Q may be a group of formula (i) or (ii).

[0071] According to any one of the above embodiments, each R 9 is a furan-2-yl group, a 1H-pyrrol-1-yl group, an optionally substituted C 6-10 It may be an aromatic group or an optionally substituted cyclohexyl group.

[0072] According to any one of the above embodiments, "aromatic group or ring" means a phenyl or naphthyl group, in particular a phenyl group.

[0073] According to any one of the above embodiments, each R 9 may be a phenyl group, a cyclohexyl group, a 3,5-dimethylphenyl group, a 3,5-di(CF3)-phenyl group, a 3,5-dimethyl-4-methoxyphenyl group.

[0074] According to any one of the above embodiments, R 10 may be a hydrogen atom.

[0075] According to any one of the above embodiments, Z may be a CMe2, SiMe2, NH or NMe group. In particular, Z may be a CMe2 group.

[0076] According to any one of the above embodiments, R 9 Non-limiting examples of possible substituents are halogen atoms, or C 1-10 The two substituents taken together are one, two, three or four groups selected from the group consisting of alkoxy, alkyl, alkenyl, pyridyl or perhalohydrocarbon groups. 4-8 A cycloalkyl group can be formed, where the term "perhalohydrocarbon" has its usual meaning in the art, such as groups like CF3. In particular, the substituents can be one or two halogen atoms, such as F or Cl, or C 1-4 It is an alkoxy or alkyl group, or a CF3 group.

[0077] According to any one of the above embodiments, the R 9 may be unsubstituted.

[0078] According to any one of the above embodiments, the ligand of formula (A) may be in racemic or optically active form.

[0079] Non-limiting examples of bidentate phosphorus ligands include 2,2'-bis((di(1H-pyrrol-1-yl)phosphanyl)oxy)-1,1'-binaphthalene, 1,1'-((naphthalen-2-yloxy)phosphanediyl)bis(1H-pyrrole), 2,2'-bis((di(1H-pyrrol-1-yl)phosphanyl)oxy)-1,1'-biphenyl, (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), 2,2'-bis((di(1H-pyrrol-1-yl)phosphanyl)oxy)-5,5',6,6',7,7',8 ,8'-Octahydro-1,1'-binaphthalene, 1,1',1'',1'''-(((2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis(oxy))bis(phosphanetryl))tetrakis(1H-pyrrole), 6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine), (oxydi-2,1-phenylene)bis(diphenylphosphine), 2,2'-bis(di phenylphosphinomethyl)-1,1'-biphenyl, 4,6-bis(diphenylphosphanyl)-10H-phenoxazine, 2-((3,3'-di-tert-butyl-2'-((4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-4H-naphtho[2,3-d][1,3,2]dioxaphosphinin-4-one, 2-((3,3'-di-tert-butyl-2'-((4,8-di-tert- Butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-8-methyl-4H-benzo[d][1,3,2]dioxaphosphinin-4-one, (1S,1'S)-(-)-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((1-naphthyl)(phenyl)phosphine), (1S,1'S)-(-)-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((4-methylphenyl)(phenyl)phosphine), 8-methyl-2-((3,3',5,5'-tetra-tert-butyl-2'-((2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy)-[1,1'-biphenyl]-2-yl)oxy)-4H-benzo[d][1,3,2]dioxaphosphinin-4-one, 2-((3,3'-di-tert-butyl-2'-((4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1, 3,2]dioxaphosphepin-6-yl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-8-isopropyl-5-methyl-4H-benzo[d][1,3,2]dioxaphosphinin-4-one, (1S,1'S)-(+)-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis((2-methoxyphenyl)(phenyl)phosphine), (1S,1'S)-(+)-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((2-methoxyphenyl)(phenyl)phosphine) (1S,1'S)-(+)-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis((2-methylphenyl)(phenyl)phosphine), (1S,1'S)-(-)-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(naphthalen-2-yl(phenyl)phosphine), (1S,1'S)-(-)-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis((4-methoxyphenyl)(phenyl)phosphine), (1S,1'S)-(-)-(2,7-di-tert-butyl-9,9-di Methyl-9H-xanthene-4,5-diyl)bis((2-naphthyl)(phenyl)phosphine), (1S,1'S)-(-)-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(naphthalen-1-yl(phenyl)phosphine), (1S,1'S)-(+)-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((2-isopropoxyphenyl)(phenyl)phosphine), (1S,1'S)-(+)-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((2-isopropylphenyl)(phenyl)phosphine) or (1S,1'S)-(-)-(2,7-di-tert.-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((dibenzo[b,d]-furan-4-yl)(phenyl)phosphine), (2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((4-methoxyphenyl)(phenyl)phosphine), (4,4' ,6,6'-tetramethoxybiphenyl-2,2'-diyl)bis{bis[3,5-bis(trifluoromethyl)phenyl]phosphine}, (6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(di(furan-2-yl)phosphane) and 3,9-bis(2,4-bis(2-phenylpropan-2-yl)phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0080] In particular, the ligand is a bidentate phosphorus ligand, such as (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), 1,1',1'',1''''-(((2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis(oxy))bis(phosphanetryl))tetrakis(1H-pyrrole), 6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxadiyl)bis(oxy)]bis(diphenylphosphine), saphosphepin), (oxydi-2,1-phenylene)bis(diphenylphosphine), 2,2'-bis(diphenylphosphinomethyl)-1,1'-biphenyl, 4,6-bis(diphenylphosphanyl)-10H-phenoxazine, 2-((3,3'-di-tert-butyl-2'-((4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-4H-naphtho[2,3-d][1,3, 2]dioxaphosphinin-4-one, 2-((3,3'-di-tert-butyl-2'-((4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-8-methyl-4H-benzo[d][1,3,2]dioxaphosphinin-4-one, (1S,1'S)-(-)-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((1-naphthyl)(furan) (1S,1'S)-(-)-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis((4-methylphenyl)(phenyl)phosphine), (6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(di(furan-2-yl)phosphane) and 3,9-bis(2,4-bis(2-phenylpropan-2-yl)phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0081] According to a particular embodiment of the invention, the bidentate phosphorus ligand is a bidentate phosphite ligand. In particular, the bidentate phosphite ligand is selected from the group consisting of 2,2'-bis(dibenzo[d,f][1,3,2]dioxaphosphepin-6-yloxy)-1,1'-biphenyl, 6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepin), 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-[1,1

[0043] The compound may be selected from the group consisting of (6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl]bis(di(furan-2-yl)phosphane), (6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(di(furan-2-yl)phosphane), and 3,9-bis(2,4-bis(2-phenylpropan-2-yl)phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0082] The phosphorus ligand can be added to the reaction medium of the method of the present invention in a wide range of concentrations. Non-limiting examples of phosphorus ligand concentration values ​​include values ​​ranging from about 0.001 mol% to about 50 mol% based on the substrate mass, preferably from about 0.005 mol% to about 50 mol% based on the substrate mass, preferably from about 0.005 mol% to about 15 mol% based on the substrate mass. As known to those skilled in the art, the optimal concentration of the phosphorus ligand depends on the nature of the phosphorus ligand, the nature of the substrate, the nature of the metal complex, the reaction temperature and the desired reaction time.

[0083] According to any one of the above embodiments, carbon monoxide and hydrogen gas can be generated in situ by methods known to those skilled in the art, for example from methyl formate, formic acid or formaldehyde. The CO / H2 gas volume ratio is 2 / 1 to 1 / 5, preferably 1 / 1 to 1 / 5, or preferably 2 / 1 to 1 / 2, preferably 1.5 / 1 to 1 / 1.5, and more preferably, this ratio is 1 / 1.

[0084] The reaction can be carried out in the presence or absence of a solvent. Where a solvent is required or used for practical reasons, any solvent currently used in such reaction types can be used for the purposes of the present invention. Non-limiting examples include C toluene, 1,3-diisopropylbenzene, cumene or pseudocumene or mixtures thereof. 6-12 These include aromatic solvents, alcoholic solvents such as methanol, ethanol, 2-methylbutan-2-ol or mixtures thereof, hydrocarbon solvents such as cyclohexane, heptane or mixtures thereof, ester solvents such as n-butyl acetate, isopropyl acetate, ethyl acetate, or ether solvents such as methyltetrahydrofuran, tetrahydrofuran or mixtures thereof. The choice of solvent depends on the nature of the substrate and / or catalyst, and the skilled person is fully capable of choosing the most suitable solvent in each case to optimize the reaction.

[0085] The hydroformylation reaction can be carried out at a temperature ranging from 50° C. to 150° C., more preferably at a temperature ranging from 80° C. to 130° C., or even at a temperature ranging from 90° C. to 110° C. Of course, the skilled person can also select the preferred temperature depending on the melting and boiling points of the starting and final products and the desired reaction time or conversion.

[0086] The hydroformylation can be carried out at CO / H2 pressures ranging from 1 bar to 50 bar, preferably from 10 bar to 50 bar, more preferably from 10 bar to 20 bar. Of course, the skilled person is fully capable of adjusting the pressure depending on the catalyst loading and the dilution of the substrate in the solvent.

[0087] According to a particular embodiment of the present invention, the hydroformylation is carried out in the presence of a diol. When the hydroformylation is carried out in the presence of a diol, a dimer may be formed. The dimer has the formula [ka] [In the formula, R1 , R 2 , R 3 , R 4 , R d and m has the same meaning as defined above] or in the form of a mixture thereof. In particular, the dimer of formula (VII) formed is at most 20%. This dimer can be converted to a compound of formula (I) as defined above for a compound of formula (II).

[0088] The compounds of formula (II) are novel compounds and exhibit many advantages as explained above and illustrated in the examples. Another subject of the invention is therefore the compounds of formula (II) [ka] [In the formula, m is 0 or 1; R 1 and R 2 are independent of each other, C 1-12 represents a hydrocarbon group, which may optionally contain 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; or R 1 and R 2 Together, C 5-18 Cycloalkyl or C 5-18 cycloalkenyl groups, each of which optionally has one or more hydroxy groups, C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 1-6 Ester, COOH, C 6-10 Aryl and / or C 6-10 R may be substituted with an aryloxy group; 3 and R 4 are each independently a hydrogen atom or C 1-6 R represents an alkyl group; c is a hydrogen atom, C 1-12 a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R c is the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (II); n is 0 or 1, R d is C 1-12 is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II a ) and the oxygen atom of formula (II) ], with the exception of 4-butyl-1-[(5,5-dibutyltetrahydro-2-furanyl)oxy]-2,4-octanediol and 2-[(tetrahydro-5,5-dimethyl-2-furanyl)oxy]ethanol.

[0089] Another subject of the invention is the preparation of compounds of formula (I) [ka] [In the formula, m is 0 or 1; R 1 is C 1-12 represents a hydrocarbon group, said group optionally containing 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; R 2 is a hydrogen atom or R 1 represents a group; or R 1 and R 2 Together, C 5-18 Cycloalkyl or C 5-18 cycloalkenyl groups, each of which optionally has one or more hydroxy groups, C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 1-6 Ester, COOH, C 6-10 Aryl and / or C 6-10R may be substituted with an aryloxy group; 3 and R 4 are each independently a hydrogen atom or C 1-6 R represents an alkyl group; c is a hydrogen atom, C 1-12 a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R c is the formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and m has the same meaning as defined in formula (II); n is 0 or 1, R d is C 1-12 is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II a ) and the oxygen atom of formula (II) or the use of a compound in the form of any one of the stereoisomers or a mixture thereof.

[0090] Typical modes for carrying out the method of the invention are reported in the following examples. EXAMPLES

[0091] The invention will now be described in more detail by the following examples, in which abbreviations have their usual meaning in the art and temperatures are given in degrees Celsius (°C). Preparation of precatalyst and ligand solutions was carried out using standard Schlenk techniques under an inert atmosphere (argon). Solvents were routinely dried and distilled under an argon atmosphere. NMR spectra were recorded on a Bruker AV 300, AV 400, or AV 500 MHz spectrometer at 20°C. Chemical shifts were expressed as solvent signals (chloroform, δ H = 7.26 ppm, δ C = 77.0 ppm. Signal assignments are 1 H, 1H-COSY, -NOESY, 13 C, 1 Confirmation was performed by recording H-HSQC and -HMBC experiments. Gas chromatography was performed on an Agilent 7890 A series equipped with an HP5 column (30 m × 0.25 mm inner diameter, 0.25 μm film thickness) and tetradecane was used as the internal standard.

[0092] [Example 1] (Hydroformylation of 4,4-dimethyl-1-vinylcyclohexan-1-ol) The autoclave was charged with 4,4-dimethyl-1-vinylcyclohexan-1-ol (74.38 g, 482.18 mmol), 1,2-ethanediol (101.24 g, 1.63 mol), 6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine) [BiPhePhos] (1.1245 mg, 0.0014 mmol), and [Rh(CO)2acac] (5 × 10 -4 The mixture was charged with 1 mmol [Rh]. The vessel was purged with H2 / CO (1:1, 4 x 5 and 2 x 10 bar), pressurized at 10 bar and heated at 75 °C with vigorous stirring for 384 h to reach 97.6% conversion. After cooling and depressurization, GLC analysis of the slightly turbid reaction mixture revealed the presence of 4,4-dimethyl-1-vinylcyclohexan-1-ol (1.85%), 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol (76.4%), 8,8-dimethyl-1-oxaspiro[4.5]decan-2-ol (1.3%), 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane (12.7%) and hydrogenated starting material (4.1%). This crude reaction mixture (186.5 g) was further processed in the next step.

[0093] 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol: [ka]

[0094] 1,2-Bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane: [ka]

[0095] [Example 2] (Preparation of (2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane from 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol and 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane) 186.5 g of a biphasic mixture of (2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane and 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane and 1,2-ethanediol was obtained from the hydroformylation reaction from 74.38 g (482.18 mmol) of 4,4-dimethyl-1-vinylcyclohexan-1-ol as reported in Example 1.

[0096] A 1,2-ethanediol phase (approximately 71.2 g) was separated from approximately 115.3 g of the product phase. This 1,2-ethanediol phase (approximately 71.2 g) was mixed with 45 g of 1,2-ethanediol, 330 g of xylene and 1.24 g (96%) of H2SO4 (2.5 mol%) in a 1 L flask equipped with a small column (2-element Sulzer EX) and a Dean-Stark apparatus. The mixture was dried and 115.3 g of the product phase was added in 2.5 h (internal temperature 130 °C-138 °C) and the water was collected (Dean-Stark apparatus). After heating for another 1.5 h (no starting material), the mixture was cooled and the 1,2-ethanediol phase was separated (99.6 g). The organic phase was washed with 160 g of saturated aqueous NaHCO3 and twice with 93 g of water. Xylene was distilled off (75 mbar, internal temperature 73° C.-110° C.). The crude (103.6 g crude) was distilled in a Vigreux column (1.5 mbar, internal temperature 145° C. at the end). 78.85 g (374.9 mmol, 77.7% yield over two steps) of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (and 3.8 g (18.1 mmol, 3.8% yield over two steps) of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane) were obtained.

[0097] (2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane: [ka]

[0098] 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane: [ka]

[0099] The use of pure 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane in the reaction (azeotropic distillation of 5 eq of 1,2-ethanediol, H2SO4 (2.5 mol%), xylene, and water) allowed to obtain the same yield for 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (77% yield, 3.8% for 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane).

[0100] [Example 3] (Production of 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal from 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane) 78.85 g (374.9 mmol) of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (and 3.8 g (18.1 mmol) of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane), 83.5 g of heptane, 125.3 g of water and 125.3 g of AcOH (5 eq) were mixed and heated at 80° C. under stirring for 4 h (72% conversion). The mixture was cooled to 0° C.-5° C. and 36% aqueous NaOH solution (69.6 g of NaOH, 139 g of water) was added in 1.5 h (internal temperature <10° C.). The aqueous phase was separated (474.7 g, pH 6). The organic phase (157.3 g) was washed with 58.2 g of saturated aqueous NaHCO3 solution and 57.2 g of water. Heptane (83.5 g) was distilled off (50-77 °C, 190-30 mbar) and the mixture was distilled in a Vigreux column. 45.2 g (272.1 mmol) of 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal and 1.6 g (9.6 mmol) of 3-(4,4-dimethylcyclohexylidene)propanal were obtained. In addition, 21.84 g (103.8 mmol) of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (and 1.13 g (5.35 mmol) of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane) were recycled (conversion yield 99.2%).

[0101] 3-(4,4-Dimethylcyclohex-1-en-1-yl)propanal [ka]

[0102] 3-(4,4-Dimethylcyclohexylidene)propanal [ka]

[0103] [Example 4] (Production of 2-methyl-1-(p-tolyl)but-3-en-2-ol from 4-methylphenylacetone) To a cooled solution (0 °C) of 139.9 mL of vinylmagnesium chloride (1.6 M in THF, 254.4 mmol, 1.1 eq) was slowly added a solution of 1-(p-tolyl)propan-2-one (37.7 g, 254.4 mmol) in 153 mL of THF. During the addition of the ketone, the internal temperature did not exceed 5 °C. The mixture was further stirred overnight (16 h) at 0 °C and analyzed by GC. The reaction mixture was slowly added to a cooled solution of 18.3 g of AcOH (305.2 mmol) in 200 mL of water. The phases were separated and the aqueous phase was extracted with 150 mL of TBME. The combined organic phases were washed with saturated aqueous NaHCO3 and saturated aqueous NaCl. After drying over Na2SO4, the solvent was evaporated under reduced pressure (500-20 mbar, 50 °C). The crude product (48.2 g) was purified by distillation through a Vigreux column under reduced pressure (oil bath 40°C-125°C, 50-4 mbar, bp 97°C / 4 mbar) to obtain 35.5 g (201.4 mmol, 79% yield) of 2-methyl-1-(p-tolyl)but-3-en-2-ol as a colorless liquid.

[0104] 2-Methyl-1-(p-tolyl)but-3-en-2-ol: In CDCl3 1The H-NMR analysis results were consistent with the data in the literature: Araki, S.; Ohmura, M.; Butsugan, Y. Bulletin of the Chemical Society of Japan(1986),59(6),2019-20.

[0105] [ka]

[0106] [Example 5] (Production of (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane from 2-((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol and 1,2-bis((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethane) In an autoclave, add 2-methyl-1-(p-tolyl)but-3-en-2-ol (12.9 g, 73.2 mmol), 1,2-ethanediol (14.17 g, 0.228 mol), and BiPhePhos solution (7.55 × 10 -4 mmol) and Rh(CO)2acac solution (2.46 × 10 -4 The vessel was purged with H2 / CO (1:1, 4 x 5 bar), pressurized to 10 bar and then heated at 90 °C with vigorous stirring at constant pressure for 24 h to reach >99% conversion. GLC analysis of the crude material revealed the presence of 2-((5-methyl-5-(4-methylbenzyl)tetra-hydrofuran-2-yl)oxy)ethan-1-ol (47%, 33%), hydrogenated starting material (7%) and some unidentified product. A portion of this crude reaction mixture (27.0 g, 80% yield, 58.6 mmol, containing 14.7 g of a mixture of 2-((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol and 1,2-bis((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethane) was further processed in the next step.

[0107] 2-((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol: [ka]

[0108] 1,2-bis((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethane: [ka]

[0109] In a 10 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g (6.5 mmol) of the mixture of (2-((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethane-1-ol and 1,2-bis((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethane) obtained in the above hydroformylation reaction (from 8.13 mmol of 2-methyl-1-(p-tolyl)but-3-en-2-ol) was stirred with 5 mL of xylene, 2.5 eq of 1,2-ethanediol (5 eq in total) and 13.1 mg (0.133 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C) and water was collected (Dean-Stark apparatus). After 3 h, complete conversion of (2-((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol and 1,2-bis((5-methyl-5-(4-methylbenzyl)tetrahydrofuran-2-yl)oxy)ethane) was observed by GC. The mixture is diluted with 10 mL MTBE and washed with 5 mL water. The organic phase was then washed with 5 mL saturated aqueous NaHCO3, once with 5 mL water and with 5 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50° C., 15 mbar). The crude was purified by column chromatography (80 g cartridge, 100% pentane to 100% MTBE). 937 mg (4.035 mmol, 62% yield) of a mixture containing (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane, (Z)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane, (E / Z)-2-(3-methyl-4-(p-tolyl)but-2-en-1-yl)-1,3-dioxolane and 2-(3-(4-methylbenzyl)but-3-en-1-yl)-1,3-dioxolane (ratio 38.5 / 31.1 / 25.4 / 4.0) was isolated.

[0110] (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane: [ka]

[0111] (Z)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane (mixture of signals): [ka]

[0112] (E)-2-(3-methyl-4-(p-tolyl)but-2-en-1-yl)-1,3-dioxolane (characteristic signals): [ka]

[0113] (Z)-2-(3-methyl-4-(p-tolyl)but-2-en-1-yl)-1,3-dioxolane (characteristic signals): [ka]

[0114] 2-(3-(4-Methylbenzyl)but-3-en-1-yl)-1,3-dioxolane (characteristic signals): [ka]

[0115] [Example 6] (Production of 2-methyl-1-(p-tolyl)but-3-en-1-ol from 4-methylbenzaldehyde) To a cooled solution (0 °C) of 494.4 mL of 1-methyl-2-propenylmagnesium chloride (0.5 M in THF, 247.2 mmol, 1.1 eq) was slowly added a solution of 4-methylbenzaldehyde (27.0 g, 224.7 mmol) in 135 mL of THF. During the addition of the aldehyde, the internal temperature did not exceed 5 °C. The mixture was further stirred overnight (16 h) at 0 °C and analyzed by GC. The reaction mixture was slowly added to a cooled solution of 16.2 g of AcOH (269.7 mmol) in 200 mL of water. The phases were separated and the aqueous phase was extracted twice with 150 mL of TBME. The combined organic phases were washed with saturated aqueous NaHCO3 and saturated aqueous NaCl. After drying over Na2SO4, the solvent was evaporated under reduced pressure (500-4 mbar, 50 °C). The crude product (44.3 g) was purified by distillation through a Vigreux column under reduced pressure (oil bath 120 °C, 900-3 mbar, bp 90 °C / 3 mbar) to obtain 39.0 g (221.3 mmol, 98.4% yield) of 2-methyl-1-(p-tolyl)but-3-en-1-ol (syn / anti mixture) as a colorless liquid.

[0116] NMR analysis in CDCl3 was consistent with literature data for the syn isomer: Shibata, I.; Yoshimura, N.; Yabu, M. Baba, A. Eur. J. Org. Chem. 2001, 3207-3211. S. Hayashi, K. Hirano, H. Yorimitsu, K. Oshima Org. Lett. 2005, 7, 16, 3577-3579.

[0117] 2-Methyl-1-(p-tolyl)but-3-en-1-ol (syn isomer): [ka]

[0118] 2-Methyl-1-(p-tolyl)but-3-en-1-ol (anti isomer): [ka]

[0119] [Example 7] (Production of (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane from 2-((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethan-1-ol and 1,2-bis((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethane) The autoclave was charged with 2-methyl-1-(p-tolyl)but-3-en-1-ol (2.02 g, 11.09 mmol), ethylene glycol (2.24 g, 36.09 mmol), Rh(CO)2acac (1.6 mg, 0.0062 mmol) and BiPhePhos (13.6 mg, 0.0173 mmol). The vessel was purged with H2 / CO (1:1, 4 x 5 bar) and pressurized at 10 bar before being heated at 90 °C with vigorous stirring at constant pressure for 24 h to reach ≥ 99% conversion. The crude reaction mixture was diluted with Et2O (25 mL) and washed with water (2 x 5 mL). The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated to give a light brown oil (2.15 g, 7.76 mmol, estimated overall yield of 2-((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethan-1-ol and 1,2-bis((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethane 70%) which was further carried on to the next step or purified by column chromatography.

[0120] 2-((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethan-1-ol: [ka]

[0121] 1,2-bis((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethane: [ka]

[0122] In a 10 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 1.18 g (4.714 mmol) of 2-((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethan-1-ol obtained in the hydroformylation reaction above was stirred with 5 mL of xylene, 2.34 g (37.7 mmol) of 1,2-ethanediol and 23.1 mg (0.133 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and water was collected (Dean-Stark apparatus). After 3 h, complete conversion of 2-((5-methyl-6-(p-tolyl)tetrahydro-2H-pyran-2-yl)oxy)ethan-1-ol was observed by GC. The mixture was diluted with 10 mL of MTBE and washed with 5 mL of water. The organic phase was then washed with 5 mL of saturated aqueous NaHCO3, once with 5 mL of water, and with 5 mL of saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50° C., 15 mbar). The crude was purified by column chromatography (80 g cartridge, 100% cyclohexane to 100% MTBE). 470 mg (2.023 mmol, 42.9% yield) of the isomeric mixture (ratio 56.3 / 27.6 / 13.0 / 3.1) was isolated (1.139 mmol of (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane (56.3%) and 0.884 mmol of the other isomers (Z)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane, (E / Z)-2-(3-methyl-4-(p-tolyl)but-2-en-1-yl)-1,3-dioxolane, 2-(3-(4-methylbenzyl)but-3-en-1-yl)-1,3-dioxolane, ratio 27.6 / 13.0 / 3.1).

[0123] [Example 8] (Production of (E)-4-methyl-5-(p-tolyl)pent-4-enal from (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane) 9.6 g (41.32 mmol) of (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane, 14.5 mL of heptane, 15 g of water and 15 g of AcOH (5 eq) were mixed and heated under stirring at 80° C. for 4 h (63% conversion). The mixture was cooled to 0° C.-5° C. and 26% aqueous NaOH (9 g NaOH, 25 g water) was added in 1.5 h (internal temperature <10° C.). The aqueous phase was separated (pH 6) and re-extracted with 15 mL of heptane. The combined organic phase was washed with 10 mL of water and 15 mL of saturated aqueous NaHCO3. The organic phase was dried over Na2SO4 and the solvent was evaporated under reduced pressure. 8.73 g of a mixture of (E)-4-methyl-5-(p-tolyl)pent-4-enal (GC 63%, 29.2 mmol, yield 71%) and (E)-2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane (GC 32%, 12.0 mmol, yield 29%) was obtained (conversion yield 99%).

[0124] (E)-4-Methyl-5-(p-tolyl)pent-4-enal In CDCl3 1 H and 13 The C NMR analysis results were consistent with literature data (R. Moretti, see WO 2010052635).

[0125] [ka]

[0126] A similar deprotection was possible with the (E / Z) mixture of 2-(3-methyl-4-(p-tolyl)but-3-en-1-yl)-1,3-dioxolane (the same yields were achieved).

[0127] (Z)-4-Methyl-5-(p-tolyl)pent-4-enal (mixture of signals): [ka]

[0128] [Example 9] (Hydroformylation of 4,4-dimethyl-1-vinylcyclohexan-1-ol in 1,3-propanediol) The autoclave was charged with 4,4-dimethyl-1-vinylcyclohexan-1-ol (4.94 g, 32.415 mmol), 1,3-propanediol (8.49 g, 111.57 mmol), BiPhePhos (39.7 mg, 0.0505 mmol), and Rh(CO)2acac (4.2 mg, 0.0163 mmol). The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and heated at 90 °C with 10 bar syngas pressure for 72 h with vigorous stirring. After cooling and depressurization, the reaction mixture was diluted with Et2O (20 ml) and washed with H2O (20 ml). The aqueous layer was decanted and extracted with a second portion of Et2O (20 ml). The recombined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated to give a yellow oil (6.75 g) which was analyzed by GLC revealing 99% conversion and the formation of hydrogenated starting material (6.6%), 8,8-dimethyl-1-oxaspiro[4.5]decan-2-ol (1.7%), 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-1-ol (55.2%) and 1,3-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propane (27.5%). The product was isolated by chromatography (Et2O / pentane, 1:1) and identified by spectrum. The crude yellow oil (5.93 g) remaining after analysis was further processed in the next step.

[0129] 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-1-ol: [ka]

[0130] 1,3-Bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propane (major isomer): [ka]

[0131] [Example 10] (Production of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane from 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-1-ol and 1,3-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propane) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 4.79 g of the crude product from Example 9 (hydroformylation reaction, 22.529 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was stirred with 25 mL of xylene, 8.67 g (112.65 mmol) of 1,3-propanediol and 55.2 mg (0.563 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and the water was collected (Dean-Stark apparatus). After 1.14 h, complete conversion of 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-1-ol and 1,3-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propane was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50° C., 15 mbar). The crude product (4.22 g, GC 93.3%) was distilled (Kugelrohr). 3.77 g (16.81 mmol) of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane and 0.201 g (0.896 mmol) of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxane were obtained (78.6% yield for the two steps).

[0132] 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane [ka]

[0133] 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxane [ka]

[0134] [Example 11] (Production of 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal from 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane) 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80° C., 4.5 h) according to the protocol of Example 3. To increase the conversion, the aqueous phase was separated, a fresh water / AcOH mixture was added, and the mixture was further heated at 80° C. (1 h, 60% conversion).

[0135] [Example 12] (Hydroformylation of 4,4-dimethyl-1-vinylcyclohexan-1-ol in 1,2-pentanediol) The autoclave was charged with 4,4-dimethyl-1-vinylcyclohexan-1-ol (4.97 g, 32.609 mmol), 1,2-pentanediol (10.43 g, 100.15 mmol), BiPhePhos (38.7 mg, 0.0492 mmol) and Rh(CO)2acac (4.3 mg, 0.0167 mmol). The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and heated at 90 °C and 10 bar syngas pressure for 48 h with vigorous stirring. After cooling and depressurization, a sample (1.13 g) of the reaction mixture (15.36 g) was diluted with Et2O (10 ml) and washed with H2O (2 x 5 ml). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to give a colorless oil (0.73 g) which was analyzed by GLC, revealing >99% conversion and the formation of hydrogenated starting material (5.6%), 8,8-dimethyl-1-oxaspiro[4.5]decan-2-ol (1.7%), 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-1-ol (10.1%), 1-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-2-ol (69.4%) and 2,2'-(pentane-1,2-diylbis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) (2.4%). The products were isolated by chromatography (Et2O / pentane, 1:1) and identified by spectra. The crude reaction mixture (14.23 g) remaining after analysis was carried further into the next step.

[0136] 2-((8,8-Dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-1-ol (major diastereomer) [ka]

[0137] 1-((8,8-Dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-2-ol (Isomer A) [ka]

[0138] 1-((8,8-Dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-2-ol (Isomer B) [ka]

[0139] 2,2'-(pentane-1,2-diylbis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) (mixture of four diastereomers) [ka]

[0140] [Example 13] (Production of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4-propyl-1,3-dioxolane from 1-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-2-ol, 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-1-ol and 2,2'-(pentane-1,2-diylbis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane)) In a 100 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 13.1 g of the crude product from Example 12 (hydroformylation reaction, 27.788 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was stirred with 50 mL of xylene, 7.235 g (69.47 mmol) of 1,2-pentanediol and 61.3 mg (0.625 mmol, 2.2 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and the water was collected (Dean-Stark apparatus). After 3 h 40 min, complete conversion of 1-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-2-ol, 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)pentan-1-ol and 2,2'-(pentane-1,2-diylbis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50 °C, 15 mbar). The crude product (6.7 g) was distilled (Kugelrohr) for purification. 5.64 g (22.37 mmol) of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4-propyl-1,3-dioxolane was obtained (80.5% yield in two steps). GC / NMR identified 2% of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-4-propyl-1,3-dioxolane.

[0141] [ka]

[0142] [Example 14] (Production of 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal from 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4-propyl-1,3-dioxolane) 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4-propyl-1,3-dioxolane was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80° C., 4.5 h) according to the protocol of Example 3. To increase the conversion, the aqueous phase was separated, fresh water / AcOH mixture was added, and the mixture was further heated at 80° C.

[0143] [Example 15] (Hydroformylation of 4,4-dimethyl-1-vinylcyclohexan-1-ol in trans-1,2-cyclohexanediol) An autoclave was charged with 4,4-dimethyl-1-vinylcyclohexan-1-ol (5.00 g, 32.804 mmol), trans-1,2-cyclohexanediol (11.78 g, 99.384 mmol). The mixture was stirred for 30 min to give a very viscous biphasic suspension. BiPhePhos (39.8 mg, 0.0506 mmol) and Rh(CO)2acac (4.1 mg, 0.0159 mmol) were then added. The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and heated at 90 °C with 10 bar syngas pressure for 48 h with vigorous stirring. After cooling and depressurization, the white crude solid reaction mass was dissolved with MeOH (5 ml) and Et2O (20 ml). The resulting solution was washed with HO (3 x 20 ml) and then the organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to give a crude oil (7.97 g) which was analyzed by GLC, revealing complete conversion and formation of hydrogenated starting material (7.9%), 8,8-dimethyl-1-oxaspiro[4.5]decan-2-ol (5.9%), 2,2'-oxybis(8,8-dimethyl-1-oxaspiro[4.5]decane) (1.7%), 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)cyclohexan-1-ol (84%) and traces of 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)cyclohexane. The products were isolated by chromatography (EtO / pentane, 1:1) and identified by spectra. The crude reaction mixture (6.88 g) remaining after analysis was carried further into the next step.

[0144] 2-((8,8-Dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)cyclohexan-1-ol (Diastereomer A) [ka]

[0145] 2-((8,8-Dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)cyclohexan-1-ol (Diastereomer B) [ka]

[0146] [Example 16] (Preparation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)hexahydrobenzo[d][1,3]dioxole from 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)cyclohexan-1-ol and 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)cyclohexane) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 2 g of the crude product from Example 15 (hydroformylation reaction, 10.0 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was stirred with 20 mL of xylene, 2.96 g (25 mmol) of trans-1,2-cyclohexanediol and 24.5 mg (0.25 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and water was collected (Dean-Stark apparatus). After 3 h 40 min, incomplete conversion of 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)cyclohexan-1-ol was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL of MTBE and washed with 10 mL of water. The organic phase was then washed with 10 mL of saturated aqueous NaHCO3, once with 10 mL of water, and with 10 mL of saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50 °C, 15 mbar). The crude product (1.6 g) was purified by column chromatography (80 g cartridge, cyclohexane / MTBE 99 / 1 to cyclohexane / MTBE) and 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)hexahydrobenzo[d][1,3]dioxole was isolated (226 mg, 0.85 mmol, 8.5% yield). GC / NMR identified 1% of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)hexahydrobenzo[d][1,3]dioxole.

[0147] 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)hexahydrobenzo[d][1,3]dioxole [ka]

[0148] 2-(2-(4,4-dimethylcyclohexylidene)ethyl)hexahydrobenzo[d][1,3]dioxole [ka]

[0149] [Example 17] (Hydroformylation of 4,4-dimethyl-1-vinylcyclohexan-1-ol in 2,3-butanediol) An autoclave was charged with 4,4-dimethyl-1-vinylcyclohexan-1-ol (4.98 g, 32.67 mmol), 2,3-butanediol (8.99 g, 99.755 mmol), BiPhePhos (39.3 mg, 0.05 mmol) and Rh(CO)2acac (4.4 mg, 0.0171 mmol). The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and heated at 90 °C and 10 bar syngas pressure for 48 h with vigorous stirring. After cooling and depressurization, a sample (1 g) of the reaction mixture (13.33 g) was diluted with Et2O (10 ml) and washed with H2O (10 ml). The aqueous layer was decanted and extracted with a second portion of Et2O (10 ml). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated to give a pale yellow oil (0.62 g) which was analyzed by GLC, revealing >99% conversion and the formation of hydrogenated starting material (5.3%), 8,8-dimethyl-1-oxaspiro[4.5]decan-2-ol (4%), 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butan-2-ol (67%) and 2,2'-oxybis(8,8-dimethyl-1-oxaspiro[4.5]decane) (1.1%). The products were isolated by chromatography (Et2O / pentane, 1:1) and identified by spectra. The crude reaction mixture (12.33 g) remaining after analysis was further processed in the next step.

[0150] 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butan-2-ol (major isomer) [ka]

[0151] [Example 18] (Preparation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4,5-dimethyl-1,3-dioxolane from 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butan-2-ol) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 4.0 g of the crude product from Example 17 (hydroformylation reaction, 9.68 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was stirred with 17 mL of xylene, 2.2 g (24.2 mmol) of 2,3-butanediol and 23.8 mg (0.242 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and the water was collected (Dean-Stark apparatus). After 1 h, complete conversion of 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butan-2-ol and 2,2'-(butane-2,3-diylbis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50 °C, 15 mbar). The crude product (2.02 g) was distilled (Kugelrohr) for purification. 1.83 g (7.659 mmol) of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4,5-dimethyl-1,3-dioxolane was obtained (79% yield over two steps). GC / NMR identified 2% of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-4,5-dimethyl-1,3-dioxolane.

[0152] 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4,5-dimethyl-1,3-dioxolane [ka]

[0153] 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-4,5-dimethyl-1,3-dioxolane [ka]

[0154] [Example 19] (Production of 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal from 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4,5-dimethyl-1,3-dioxolane) 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4,5-dimethyl-1,3-dioxolane was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80° C., 4.5 h) according to the protocol of Example 3. To increase the conversion, the aqueous phase was separated, fresh water / AcOH mixture was added, and the mixture was further heated at 80° C.

[0155] [Example 20] (Hydroformylation of 4,4-dimethyl-1-vinylcyclohexan-1-ol in MeOH) The autoclave was charged with 4,4-dimethyl-1-vinylcyclohexan-1-ol (497.13 g, 3.26 mol), MeOH (365.94 g, 11.41 mol), BiPhePhos solution (4 ml, 15.52 mg, 0.0197 mmol in 4,4-dimethyl-1-vinylcyclohexan-1-ol, 3.542 g, 22.9601 mmol) and Rh(CO)2acac solution (3.2 ml, 1.67 mg, 0.0065 mmol in 4,4-dimethyl-1-vinylcyclohexan-1-ol, 2.846 g, 18.4506 mmol). The vessel was purged with nitrogen (3×5 bar, no stirring) and then with H2 / CO 1:1 (5×10 bar, no stirring). The reactor was pressurized to 10 bar and the mixture was heated at constant pressure with vigorous stirring at 90° C. for 48 h. After cooling and depressurization, analysis of the crude material by GLC revealed 96.6% conversion and the formation of hydrogenated starting material (2.6%), 8,8-dimethyl-1-oxaspiro[4.5]decan-2-ol (1.4%), 2,2′-oxybis(8,8-dimethyl-1-oxaspiro[4.5]decane) (0.4%) and 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane (92%). To achieve complete conversion of the remaining starting material, BiPhePhos solution (2 ml, 7.76 mg, 0.0099 mmol in 4,4-dimethyl-1-vinylcyclo-hexan-1-ol, 1.77 g, 11.4749 mmol) and [Rh(CO)2acac solution (1.5 ml, 0.78 mg, 0.003 mmol in 4,4-dimethyl-1-vinylcyclohexan-1-ol, 1.33 g, 8.6224 mmol) were injected and the hydroformylation was continued at 6.5 bar and 90° C. for 21 h. After cooling and depressurization, the crude emulsion (approximately 955.16 g) was analyzed by GLC, which revealed complete conversion (>99.5%) and the formation of hydrogenated starting material (2.6%), 8,8-dimethyl-1-oxaspiro[4.5]decan-2-ol (1.3%), 2,2'-oxybis(8,8-dimethyl-1-oxaspiro[4.5]decane) (0.3%) and 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane (95.3%).To isolate the major product, a sample of the crude reaction mixture (250 mg) was diluted with Et2O (5 mL) and washed with H2O (2 mL). The aqueous layer was decanted and the organic solution was dried over anhydrous sodium sulfate, filtered, and concentrated to give nearly pure 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane (93 mg) suitable for spectral analysis. The remaining 952.96 g of the crude reaction mixture (2 phases) was carried on to the next step.

[0156] 2-Methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane [ka]

[0157] [Example 21] (Preparation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude material from example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of toluene, 5.37 g (51.54 mmol) of 2,2-dimethyl-1,3-propanediol and 25.3 mg (0.258 mmol, 2.5 mol%) (98%) of H2SO4 after MeOH evaporation. After stirring at 50 °C, the formation of 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)-2,2-dimethylpropan-1-ol and 2,2'-((2,2-dimethylpropane-1,3-diyl)bis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) was observed by GC and GC-MS (30 min). The mixture was heated to reflux and water was collected (Dean-Stark apparatus). After 1 h, complete conversion of 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)-2,2-dimethylpropan-1-ol and 2,2'-((2,2-dimethylpropane-1,3-diyl)bis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50° C., 15 mbar). The crude product (2.51 g) was distilled (Kugelrohr) for purification. 2.245 g (8.895 mmol) of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane and 88 mg (0.348 mmol) of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-5,5-dimethyl-1,3-dioxane) were obtained (86% yield for two steps).

[0158] 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane [ka]

[0159] 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-5,5-dimethyl-1,3-dioxane [ka]

[0160] The resulting product was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80 °C, 4-6 h) following the protocol of Example 3. To increase the conversion, the aqueous phase was separated, a fresh water / AcOH mixture was added, and the mixture was further heated at 80 °C. This procedure could be repeated several times.

[0161] [Example 22] (Preparation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude material from example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of toluene, 1.61 g (15.46 mmol) of 2,2-dimethyl-1,3-propanediol and 25.3 mg (0.258 mmol, 2.5 mol%) (98%) of H2SO4 after MeOH evaporation. After stirring at 50 °C, the formation of 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)-2,2-dimethylpropan-1-ol and 2,2'-((2,2-dimethylpropane-1,3-diyl)bis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) was observed by GC and GC-MS (30 min). The mixture was heated to reflux and water was collected (Dean-Stark apparatus). After 15 min, complete conversion of 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)-2,2-dimethylpropan-1-ol and 2,2'-((2,2-dimethylpropane-1,3-diyl)bis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) was observed by GC and the mixture was stirred for another 15 min. After cooling to room temperature, 2105 mg of decane was added for yield determination using an internal standard, giving 2.196 g (8.70 mmol, 84.4% yield over two steps) of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane and 155 mg (0.614 mmol, 6.0% yield over two steps) of 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-5,5-dimethyl-1,3-dioxane.

[0162] [Example 23] (Preparation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane - Acid Screening) General procedure for testing several acids: In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude product from Example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of xylene, 3.22 g (30.92 mmol) of 2,2-dimethyl-1,3-propanediol and catalyst after MeOH evaporation. After stirring at 50 °C, the formation of 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)-2,2-dimethylpropan-1-ol and 2,2'-((2,2-dimethylpropane-1,3-diyl)bis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) was observed by GC and GC-MS (30 min). The mixture was heated to reflux and the water was collected (Dean-Stark apparatus). After complete conversion of 3-((8,8-dimethyl-1-oxaspiro[4.5]decane-2-yl)oxy)-2,2-dimethylpropan-1-ol and 2,2'-((2,2-dimethylpropane-1,3-diyl)bis(oxy))bis(8,8-dimethyl-1-oxaspiro[4.5]decane) was observed by GC, the mixture was cooled to room temperature and 2105 mg of decane was added for yield determination using an internal standard.

[0163] Acid: 150 mg of Clay F24X (138°C for 1 hour): The yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-5,5-dimethyl-1,3-dioxane (ratio 93.2 / 6.8) was estimated to be 85%.

[0164] Acid: 150 mg of Clay F21X (138°C for 1 hour): The yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-5,5-dimethyl-1,3-dioxane (ratio 93 / 7) was estimated to be 85%.

[0165] Acid: 150 mg of zeolite CBV780 (138°C for 30 min) 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-5,5-dimethyl-1,3-dioxane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-5,5-dimethyl-1,3-dioxane (ratio 95.7 / 4.3) was obtained with a yield of 88.7%.

[0166] [Example 24] (Preparation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxepane from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane using 1,4-butanediol) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude material from example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of toluene, 4.64 g (51.54 mmol) of 1,4-butanediol and 25.3 mg (0.258 mmol, 2.5 mol%) (98%) of H2SO4 after MeOH evaporation. After stirring at 50 °C, the complete formation of 4-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butan-1-ol and 1,4-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butane from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane was observed by GC and GC-MS (15 min). The mixture was heated to reflux for 3 h and the water was collected (Dean-Stark apparatus). After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50 °C, 15 mbar). The crude product (2.06 g) was purified by column chromatography (80 g cartridge, cyclohexane / MTBE 98 / 2 to MTBE) and 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxepane (373 mg, 1.57 mmol, 15% yield), 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxepane (12 mg, 0.0516 mmol, 0.5% yield) were isolated. The starting materials (4-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butan-1-ol and 1,4-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butane) were isolated and could be reused in the same reaction.

[0167] 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxepane [ka]

[0168] 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxepane [ka]

[0169] 4-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butan-1-ol [ka]

[0170] 1,4-Bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)butane [ka]

[0171] The resulting product was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80 °C, 4-6 h) following the protocol of Example 3. To increase the conversion, the aqueous phase was separated, a fresh water / AcOH mixture was added, and the mixture was further heated at 80 °C. This procedure could be repeated several times.

[0172] [Example 25] (Preparation of 3-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,5-dihydrobenzo[e][1,3]dioxepin from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane using 1,2-benzenedimethanol) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude product of Example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of toluene, 4.4 g (30.9 mmol) of 1,2-benzenedimethanol and 25.3 mg (0.258 mmol, 2.5 mol%) (98%) of H2SO4 after MeOH evaporation. After stirring at 50 °C, the complete formation of (2-(((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)methyl)phenyl)methanol and 1,2-bis(((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)methyl)benzene was observed by GC and GC-MS (15 min). The mixture was heated to reflux and the water was collected (Dean-Stark apparatus). After 15 min, formation of 3-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,5-dihydrobenzo[e][1,3]dioxepin was observed (GC 60%). Small amounts of 3-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,5-dihydrobenzo[e][1,3]dioxepin were detected by GC / NMR.

[0173] After workup (NaHCO3, water) and column chromatography, a sample was isolated: 3-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,5-dihydrobenzo[e][1,3]dioxepin [ka]

[0174] 3-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,5-dihydrobenzo[e][1,3]dioxepin [ka]

[0175] The resulting product was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80 °C, 4-6 h) following the protocol of Example 3. To increase the conversion, the aqueous phase was separated, a fresh water / AcOH mixture was added, and the mixture was further heated at 80 °C. This procedure could be repeated several times.

[0176] [Example 26] (Preparation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4H-benzo[d][1,3]dioxine from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane using 2-hydroxybenzyl alcohol) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude product of Example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of toluene, 6.4 g (51.5 mmol) of 2-hydroxybenzyl alcohol and 351 mg (2.58 mmol, 25 mol%) of KHSO4 after MeOH evaporation. After stirring at 50 °C, the complete formation of 2-(((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)methyl)phenol, 2-((2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)benzyl)oxy)-8,8-dimethyl-1-oxaspiro[4.5]decane was observed by GC and GC-MS (15 min). The mixture was heated to reflux and the water was collected (Dean-Stark apparatus). After 15 min, 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-4H-benzo[d][1,3]dioxine was formed (GC 42%).

[0177] After workup (NaHCO3, water) and column chromatography, a sample was isolated: 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4H-benzo[d][1,3]dioxine [ka]

[0178] The resulting product was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80 °C, 4-6 h) following the protocol of Example 3. To increase the conversion, the aqueous phase was separated, a fresh water / AcOH mixture was added, and the mixture was further heated at 80 °C. This procedure could be repeated several times.

[0179] [Example 27] (Preparation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4,7-dihydro-1,3-dioxepine from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane using (Z)-but-2-ene-1,4-diol) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude material from example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of toluene, 4.54 g (51.54 mmol) of (Z)-but-2-ene-1,4-diol and 25.3 mg (0.258 mmol, 2.5 mol%) (98%) of H2SO4 after MeOH evaporation. After stirring at 50 °C, complete formation of (Z)-4-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)but-2-en-1-ol and (Z)-1,4-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)but-2-ene from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane was observed by GC and GC-MS (15 min). The mixture was heated to reflux and water was collected (Dean-Stark apparatus).

[0180] After workup (NaHCO3, water) and column chromatography, a sample was isolated: 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-4,7-dihydro-1,3-dioxepin [ka]

[0181] 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-4,7-dihydro-1,3-dioxepin [ka]

[0182] The resulting product was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80 °C, 4-6 h) following the protocol of Example 3. To increase the conversion, the aqueous phase was separated, a fresh water / AcOH mixture was added, and the mixture was further heated at 80 °C. This procedure could be repeated several times.

[0183] [Example 28] (Production of 3,9-bis(2-(4,4-dimethylcyclohexyl-1-en-1-yl)ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane using pentaerythritol) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude product from example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of toluene, 1.43 g (10.308 mmol) of pentaerythritol and 1.43 g (10.308 mmol, 1 eq) of KHSO4 after MeOH evaporation. After stirring at 50 °C, the formation of 2-(((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)methyl)-2-(hydroxymethyl)propane-1,3-diol, (2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane-5,5-diyl)dimethanol and 2,2-bis(((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)methyl)propane-1,3-diol was observed by GC and GC-MS (15 min). The mixture was heated to reflux and the water was collected (Dean-Stark apparatus). After 2 h, the formation of 3,9-bis(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (GC 86%) and (2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane-5,5-diyl)dimethanol (GC 7%) was observed (2% of 3,9-bis(2-(4,4-dimethylcyclohexylidene)ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane) by NMR analysis.

[0184] After workup (NaHCO3, water) and column chromatography, a sample was isolated: 3,9-Bis(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane [ka]

[0185] 3,9-Bis(2-(4,4-dimethylcyclohexylidene)ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane [ka]

[0186] 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxane-5,5-diyl)dimethanol [ka]

[0187] The resulting product was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80 °C, 4-6 h) following the protocol of Example 3. To increase the conversion, the aqueous phase was separated, a fresh water / AcOH mixture was added, and the mixture was further heated at 80 °C. This procedure could be repeated several times.

[0188] [Example 29] (Production of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxan-5-ol / (2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolan-4-yl)methanol from 2-methoxy-8,8-dimethyl-1-oxaspiro[4.5]decane using 1,2,3-propanetriol) In a 50 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of crude product from Example 20 (obtained from 10.308 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was mixed with 20 mL of xylene, 2.85 g (51.54 mmol) of 1,2,3-propanetriol and 25.3 mg (0.258 mmol, 2.5 mol%) (98%) of H2SO4 after MeOH evaporation. After stirring at 50 °C, the formation of 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propane-1,2-diol and 1,3-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-2-ol was observed by GC and GC-MS (15 min). The mixture was heated to reflux and the water was collected (Dean-Stark apparatus, 2 eq of 1,2,3-propanetriol was added after 2 h). After 3 h (more 1,2,3-propanetriol was added during heating), quantitative formation of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxan-5-ol / (2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolan-4-yl)methanol was observed (GC 97%, 2.26 g crude after workup, 2.11 g (8.78 mmol) after distillation, 85% yield for two steps). 2% 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxan-5-ol / (2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolan-4-yl)methanol was observed by GC / NMR.

[0189] After workup (NaHCO3, water) and column chromatography, a sample was isolated: 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxan-5-ol / (2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolan-4-yl)methanol [ka]

[0190] 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxan-5-ol / (2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolan-4-yl)methanol [ka]

[0191] The resulting product was converted to 3-(4,4-dimethylcyclohex-1-en-1-yl)propanal (80 °C, 4-6 h) following the protocol of Example 3. To increase the conversion, the aqueous phase was separated, a fresh water / AcOH mixture was added, and the mixture was further heated at 80 °C. This procedure could be repeated several times.

[0192] [Example 30] (Hydroformylation of 4,4-dimethyl-1-vinylcyclohexan-1-ol in glycerol) Add 4,4-dimethyl-1-vinylcyclohexan-1-ol (7.54 g, 48.882 mmol), glycerol (13.65 g, 148.22 mmol), BiPhePhos (0.1148 mg, 1 × 10 -4 mmol) and Rh(CO)2acac (0.0125 mg, 4.86 × 10 -5The vessel was purged with H2 / CO 1:1 (4 x 5 bar), pressurized at 10 bar and heated at 90 °C with vigorous stirring for 60 h to reach 93.6% conversion. After cooling and depressurization, the crude mixture was diluted with Et2O (20 ml), washed with H2O (20 ml), the aqueous layer was decanted and extracted with a second portion of Et2O (20 ml). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated to give 11.24 g of residue. GLC analysis of the residue revealed the presence of starting material (6.3%), 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propane-1,2-diol (44.7%), 1,3-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-2-ol (33.5%) and hydrogenated starting material (6.6%).

[0193] 3-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propane-1,2-diol and 1,3-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-2-ol were isolated by chromatography (EtO / pentane 1:1) and identified by spectra.

[0194] 3-((8,8-Dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propane-1,2-diol (mixture of isomers) [ka]

[0195] 1,3-Bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)propan-2-ol [ka]

[0196] [Example 31] (Hydroformylation of 4-(tert-butyl)-1-vinylcyclohexan-1-ol) The autoclave was charged with 4-tert-butyl-1-vinylcyclohexanol mixture (5.04 g, 27.647 mmol, 43 / 51 cis / trans), 1,2-ethanediol (5.98 g, 96.343 mmol), BiPhePhos (32.9 mg, 0.0418 mmol) and Rh(CO)2acac (3.8 mg, 0.0147 mmol). The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and pressurized to 10 bar before being heated at 90 °C under constant pressure and vigorous stirring for 48 h to reach >99% conversion. A sample (1.65 g) of the crude solid reaction mixture (10.89 g) was dissolved in Et2O (20 ml) and washed with water (10 ml). The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated to give a white pasty solid (1.27 g) which, when analyzed by GLC, contained the hydrogenated starting material 4-(tert-butyl)-1-ethylcyclohexan-1-ol (4.1%), 2-(((2RS,5s,8RS)- and 2-(((2SR,5r,8RS)-8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol (80.4%), 1,2-bis(((2S The presence of a mixture of (R,5r,8RS)-8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethane (approximately 5-7%) and 8-(tert-butyl)-1,4-dioxaspiro[4.5]decane (5-7%, due to impurities in the starting material) was revealed. The product was isolated by chromatography (Et2O / pentane 1:1) and identified by spectroscopy. The crude reaction mixture (9.24 g) remaining after analysis was further processed in the next step.

[0197] 2-(((2RS,5s,8RS)-8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol [ka]

[0198] 2-(((2SR,5r,8RS)-8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol [ka]

[0199] 1,2-Bis(((2SR,5r,8RS)-8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethane [ka]

[0200] [Example 32] (Preparation of 2-(2-(4-(tert-butyl)cyclohex-1-en-1-yl)ethyl)-1,3-dioxolane from 2-((8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol and 1,2-bis((8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethane) In a 100 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 9.24 g of the crude product from Example 31 (hydroformylation reaction, 22.001 mmol of 4-tert-butyl-1-vinyl-cyclohexanol) was stirred with 20 mL of xylene, 6.83 g (110.01 mmol) of ethylene glycol and 54.9 mg (0.55 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and the water was collected (Dean-Stark apparatus). After 3 h, 97% conversion of 2-((8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol and 1,2-bis((8-(tert-butyl)-1-oxaspiro[4.5]decan-2-yl)oxy)ethane was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50° C., 15 mbar). The crude (5.37 g) was distilled (Kugelrohr) for purification. 3.445 g (14.452 mmol) of 2-(2-(4-(tert-butyl)cyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (66% yield over two steps) and 244 mg (1.023 mmol, 5% yield over two steps) of 2-(2-(4-(tert-butyl)cyclohexylidene)ethyl)-1,3-dioxolane) were obtained.

[0201] 2-(2-(4-(tert-butyl)cyclohex-1-en-1-yl)ethyl)-1,3-dioxolane [ka]

[0202] 2-(2-(4-(tert-butyl)cyclohexylidene)ethyl)-1,3-dioxolane [ka]

[0203] [Example 33] (Production of 3-(4-(tert-butyl)cyclohex-1-en-1-yl)propanal) This compound was prepared following the procedure reported in Example 3 using the compound prepared in Example 32 as the starting material.

[0204] In CDCl3 1 H and 13 The C-NMR analysis results were in agreement with the data in the literature (B. Winter, EP 1 054 053 A1).

[0205] [Example 34] (Hydroformylation of (1RS,3SR)- and (1SR,3SR)-3-isopropyl-1-vinylcyclohexan-1-ol) The autoclave was charged with freshly distilled (1RS,3SR)- and (1SR,3SR)-3-isopropyl-1-vinylcyclohexan-1-ol (5.01 g, 29.772 mmol, 39.6 / 48.3 diastereomeric mixture, contaminated with ca. 10% cis / trans-4-isopropyl-1-vinylcyclohexan-1-ol), 1,2-ethanediol (6.46 g, 104.08 mmol), BiPhePhos (35.4 mg, 0.045 mmol) and Rh(CO)2acac (3.9 mg, 0.0151 mmol). The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and pressurized to 10 bar, then heated at 90 °C with vigorous stirring at constant pressure for 48 h to reach ≥ 99% conversion. The crude mixture (ca. 12 g) was diluted with Et2O (50 ml) and washed with water (2 x 20 ml). The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated to give a yellow oil (5.9 g) which was analyzed by GLC revealing the presence of a mixture of 2-((7-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol (81.5%) and only traces of 1,2-bis((7-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane. cis / trans-4-Isopropyl-1-vinylcyclohexan-1-ol was also converted to 2-((8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol (ca. 12%). The crude reaction mixture (5.9 g) was further processed in the next step.

[0206] 2-((7-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol (four diastereomers) [ka]

[0207] [Example 35] (Production of 2-(2-(5-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane and 2-(2-(3-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane from 2-((7-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol and 1,2-bis((7-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane) In a 100 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 5.01 g of the crude product obtained in Example 34 (hydroformylation reaction, 26.795 mmol of 3-isopropyl-1-vinylcyclohexan-1-ol and 2.98 mmol of cis / trans-4-isopropyl-1-vinylcyclohexan-1-ol) was stirred with 50 mL of xylene, 8.32 g (133.97 mmol) of ethylene glycol and 66.7 mg (0.67 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and water was collected (Dean-Stark apparatus). After 2 h, complete conversion of 2-((7-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol and 1,2-bis((7-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50° C., 15 mbar). The crude (5.23 g) was distilled (Kugelrohr) for purification. 3.57 g (15.913 mmol) of 2-(2-(5-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane and 2-(2-(3-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (approximately a 1 / 1 mixture, 59% yield over two steps, and 307 mg (1.36 mmol, 5% yield over two steps) of 2-(2-(3-isopropylcyclohexylidene)ethyl)-1,3-dioxolane) were obtained. 368 mg (1.64 mmol) of 2-(2-(4-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane was also isolated.

[0208] 2-(2-(5-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(3-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane 1 / 1 mixture [ka]

[0209] 2-(2-(5-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane [ka]

[0210] 2-(2-(3-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane [ka]

[0211] 2-(2-(4-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (characterized from a mixture) [ka]

[0212] [Example 36] (Production of 3-(5-isopropylcyclohex-1-en-1-yl)propanal / 3-(3-isopropylcyclohex-1-en-1-yl)propanal / and 10% of (3-(4-isopropylcyclohex-1-en-1-yl)propanal) This compound (approximately a 1 / 1 mixture) was prepared according to the procedure reported in Example 3, using the compound prepared in Example 36 as the starting material. 1 H and 13 The C-NMR analysis results were consistent with the data in the literature (R. Moretti, A. Birkbeck, International Publication No. 2017046071).

[0213] [Example 37] (Hydroformylation of 4-isopropyl-1-vinylcyclohexan-1-ol) The autoclave was charged with 4-isopropyl-1-vinylcyclohexan-1-ol (5.08 g, 30.188 mmol, 35 / 59 cis / trans), 1,2-ethanediol (6.56 g, 105.69 mmol), BiPhePhos (36.3 mg, 0.0461 mmol) and Rh(CO)2acac (4.3 mg, 0.0167 mmol). The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and pressurized to 10 bar before being heated at 90 °C with vigorous stirring at constant pressure for 48 h to reach >99% conversion. Analysis of the crude yellow oil (11.2 g) by GLC revealed the presence of a mixture of hydrogenated starting materials cis / trans 4-isopropyl-1-vinylcyclohexan-1-ol (approximately 2% / 4%), 2-((-8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol (20% / 36%) and 1,2-bis((-8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane (4.2% / 7.3% / 5% / 3.9% / 3.9%). The product was isolated by chromatography (Et2O / pentane 1:1) and identified by spectrum. Of the stereoisomers 1,2-bis((-8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane, only the stereochemical structure of 1,2-bis(((2SR,5r,8RS)-8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane could be accurately assigned. The crude reaction mixture (10.2 g) remaining after analysis was further processed in the next step.

[0214] 2-(((2RS,5s,8RS)-8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol [ka]

[0215] 2-(((2SR,5r,8RS)-8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol [ka]

[0216] 1,2-Bis(((2SR,5r,8RS)-8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane [ka]

[0217] [Example 38] (Preparation of 2-(2-(4-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane from 2-((8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol and 1,2-bis((8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane) In a 100 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 10.2 g of the crude product from Example 37 (hydroformylation reaction, 26.124 mmol of 4-isopropyl-1-vinylcyclohexan-1-ol) was stirred with 20 mL of xylene, 8.11 g (130.6 mmol) of ethylene glycol and 64.1 mg (0.65 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and water was collected (Dean-Stark apparatus). After 4 h, 97% conversion of 2-((8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane-1-ol and 1,2-bis((8-isopropyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50° C., 15 mbar). The crude product (5.02 g) was distilled (Kugelrohr) for purification. 3.37 g (15.022 mmol) of 2-(2-(4-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (58% yield over two steps) and 279 mg (1.24 mmol, 5% yield over two steps) of 2-(2-(4-isopropylcyclohexylidene)ethyl)-1,3-dioxolane were obtained.

[0218] 2-(2-(4-isopropylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane [ka]

[0219] 2-(2-(4-isopropylcyclohexylidene)ethyl)-1,3-dioxolane [ka]

[0220] [Example 39] (Production of 3-(4-isopropylcyclohex-1-en-1-yl)propanal) This compound was prepared according to the procedure reported in Example 3, starting from the compound prepared in Example 38. 1 H and 13 The C-NMR analysis results were consistent with the data in the literature (E. Singer, B. Holscher, US Patent Application Publication No. 2013 / 90390, 2013, A1).

[0221] [Example 40] (Hydroformylation of 3-isopropyl-1-vinylcyclopentanol) The autoclave was charged with (1RS,3SR)- / (1RS,3RS)-3-isopropyl-1-vinylcyclopentanol (5.04 g, 32.48 mmol, (1RS,3SR)- / (1RS,3RS)=54.6 / 42.1), 1,2-ethanediol (7.17 g, 115.51 mmol), Rh(CO)2acac (4.2 mg, 0.0163 mmol) and BiPhePhos (34.4 mg, 0.0488 mmol). The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and pressurized to 10 bar before being heated at 90 °C with vigorous stirring at constant pressure for 48 h to reach >99% conversion. A sample (250 mg) of the crude mixture (11.39 g) was diluted with Et2O (2 ml) and washed with water (2 x 1 ml). The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated to give a pale yellow oil (128.1 mg). Spectroscopic analysis of the pale yellow oil revealed the presence of 2-((7-isopropyl-1-oxaspiro[4.4]nonan-2-yl)oxy)ethan-1-ol (62.2%) and 1,2-bis((7-isopropyl-1-oxaspiro[4.4]nonan-2-yl)oxy)ethane (25%). The crude reaction mixture (11.14 g) remaining after analysis was further processed in the next step.

[0222] 2-((7-isopropyl-1-oxaspiro[4.4]nonan-2-yl)oxy)ethan-1-ol (four isomers) [ka]

[0223] 1,2-Bis((7-isopropyl-1-oxaspiro[4.4]non-2-yl)oxy)ethane (mixture of complex isomers) [ka]

[0224] [Example 41] (Production of 2-(2-(4-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane and 2-(2-(3-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane from 2-((7-isopropyl-1-oxaspiro[4.4]nonan-2-yl)oxy)ethan-1-ol and 1,2-bis((7-isopropyl-1-oxaspiro[4.4]nonan-2-yl)oxy)ethane) In a 100 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 3.0 g of the crude product from Example 40 (hydroformylation reaction, 8.32 mmol of 3-isopropyl-1-vinylcyclopentanol) was stirred with 20 mL of xylene, 1.03 g (16.64 mmol) of ethylene glycol and 20.4 mg (0.208, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and water was collected (Dean-Stark apparatus). After 3 h, complete conversion of 2-((7-isopropyl-1-oxaspiro[4.4]nonan-2-yl)oxy)ethane-1-ol and 1,2-bis((7-isopropyl-1-oxaspiro[4.4]nonan-2-yl)oxy)ethane was observed by GC. After cooling to room temperature, 1.45 g of decane was added for yield determination using an internal standard. 727 mg (3.456 mmol) of 2-(2-(4-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane and 545 mg (2.59 mmol) of 2-(2-(3-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane (72% yield over two steps) and 116 mg (0.55 mmol) of 2-(2-(3-isopropylcyclopentylidene)ethyl)-1,3-dioxolane, 7% yield over two steps were obtained.

[0225] 2-(2-(4-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(3-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane approximately 1 / 1 mixture [ka]

[0226] [ka]

[0227] Signals characteristic of 2-(2-(4-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane: [ka]

[0228] Signals characteristic of 2-(2-(3-isopropylcyclopent-1-en-1-yl)ethyl)-1,3-dioxolane: [ka]

[0229] Characteristic signals for 2-(2-(3-isopropylcyclopentylidene)ethyl)-1,3-dioxolane: [ka]

[0230] [Example 42] (Production of 3-(4-isopropylcyclopent-1-en-1-yl)propanal / 3-(3-isopropylcyclopent-1-en-1-yl)propanal) This compound (as a mixture) was prepared following the procedure reported in Example 3 using the compound prepared in Example 41 as the starting material.

[0231] 3-(4-isopropylcyclopent-1-en-1-yl)propanal / 3-(3-isopropylcyclopent-1-en-1-yl)propanal approximately 1 / 1 mixture [ka]

[0232] 3-(4-isopropylcyclopent-1-en-1-yl)propanal [ka]

[0233] 3-(3-isopropylcyclopent-1-en-1-yl)propanal [ka]

[0234] [Example 43] (Hydroformylation of cis / trans-4-butyl-1-vinylcyclohexan-1-ol) The autoclave was charged with cis / trans-4-butyl-1-vinylcyclohexan-1-ol (5.01 g, 27.48 mmol, c / t=39 / 61), 1,2-ethanediol (6.05 g, 97.47 mmol), BiPhePhos (0.00066 mmol) and Rh(CO)2acac (0.00021 mmol). The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and pressurized at 10 bar before being heated at 90 °C under constant pressure and vigorous stirring for 60 h to reach 96% conversion. The product mixture (10.48 g) consisted of cis / trans starting material (2.5%, 1.3%), hydrogenated starting material (0.36%), and 2-((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol (27.9%, 45.4%). 20% of 1,2-bis((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane was identified by GC / GCMS. The two diastereomers of 2-((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol were isolated by column chromatography on silica gel (pentane / Et2O - 1 / 1) and identified by spectra.

[0235] Cis-2-((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol [ka]

[0236] Trans-2-((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol [ka]

[0237] [Example 44] (Preparation of 2-(2-(4-butylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane from 2-((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol and 1,2-bis((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane) In a 100 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 5 g of the crude product from Example 43 (hydroformylation reaction, 13.11 mmol of 4-butyl-1-vinylcyclohexan-1-ol) was stirred with 20 mL of xylene, 8.11 g (130.6 mmol) of ethylene glycol and 64.1 mg (0.65 mmol, 2.5 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C and water was collected (Dean-Stark apparatus). After 4 h, 97% conversion of 2-((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane-1-ol and 1,2-bis((8-butyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane was observed by GC. After cooling to room temperature, the mixture was diluted with 20 mL MTBE and washed with 10 mL water. The organic phase was then washed with 10 mL saturated aqueous NaHCO3, once with 10 mL water and with 10 mL saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (50° C., 15 mbar).

[0238] The crude material (3.12 g) was purified by column chromatography (80 g cartridge, cyclohexane to cyclohexane / MTBE 90 / 10 to cyclohexane / MTBE 50) to give 1.95 g (8.12 mmol) of 2-(2-(4-butylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (62% yield over two steps) and 175 mg (0.73 mmol, 6% yield over two steps) of 2-(2-(4-butylcyclohexylidene)ethyl)-1,3-dioxolane).

[0239] 2-(2-(4-butylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane [ka]

[0240] Characteristic signals for 2-(2-(4-butylcyclohexylidene)ethyl)-1,3-dioxolane: 13 C NMR (125MHz, CDCl3): 114.0ppm.

[0241] [Example 45] (Production of 3-(4-butylcyclohex-1-en-1-yl)propanal) This compound was prepared according to the procedure reported in Example 3, starting from the compound prepared in Example 44. 1 H and 13 The C-NMR analysis results were consistent with the data in the literature (R. Moretti, WO 2019185599).

[0242] [Example 46] (Production of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane from 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol and 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane using various catalysts) General procedure for testing several acids and Lewis acids: In a 100 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 2.0 g of the crude product from Example 1 (hydroformylation reaction, 5.13 mmol of 4,4-dimethyl-1-vinylcyclohexan-1-ol) was stirred with 20 mL of xylene, 1.12 g (18.03 mmol) of ethylene glycol and acid or Lewis acid. The mixture was heated to reflux and water was collected (Dean-Stark apparatus). After complete conversion of 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane-1-ol and 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane was observed by GC, the mixture was cooled to room temperature and 831 mg of decane was added for yield measurement with an internal standard.

[0243] Acid: 382.4mg (5mol%) Cu(OTf)2 (138℃, 2h 5mol%, 2h 20mol%): A 62% yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 95.6 / 4.4) was obtained.

[0244] Acid: 170 mg (5 mol%) Bi(OTf)3 (1 hour at 138°C): A 77.4% yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 95.5 / 4.5) was obtained.

[0245] Acid: 367mg (20mol%) SnCl4 (138℃, 2h 5mol%, 2h 10mol%, 4h 20mol%): A 84.5% yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 94.3 / 5.7) was obtained.

[0246] Acid: 58mg (20mol%) ZnBr2 (138℃, 3h): 17% 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane and unreacted starting material 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol were observed by GC.

[0247] Acid: 96 mg (5 mol%) Zn(OTf)2 (4 h at 138 °C): A 76% yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 95.7 / 4.3) was obtained.

[0248] Acid: 200.8 mg (20 mol%) BF3·(AcOH)2 (4 h at 138 °C): A 67% yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 94 / 6) was obtained.

[0249] Acid: 168mg (20mol%) FeCl3 (138℃, 1h 5mol%, 2h 20mol%): 30% 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane and unreacted starting material 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol were observed by GC.

[0250] Acid: 68mg (2.5mol%) Fe(OTf)3 (138℃, 4h): A 86.2% yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 95.8 / 4.2) was obtained.

[0251] Acid: 154mg (5mol%) Fe(OTs)3 (138℃, 8h): A 80.1% yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 95.5 / 4.5) was obtained.

[0252] Acid: 19.4mg (2.5mol%) TfOH (138℃, 5h): A 90.0% yield of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 94.7 / 5.3) was obtained.

[0253] Acid: 80mg Amberlyst 15 dry (138℃, 4h): A yield of 85.4% of 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane / 2-(2-(4,4-dimethylcyclohexylidene)ethyl)-1,3-dioxolane (ratio 94.5 / 5.5) was obtained (conversion rate 96%).

[0254] [Example 47] (Hydroformylation of 1-(1-butoxyethoxy)-4,4-dimethyl-1-vinylcyclohexane) In an autoclave, add 1-(1-butoxyethoxy)-4,4-dimethyl-1-vinylcyclohexane (5.01 g, 19.693 mmol), 1,2-ethanediol (3.84 g, 61.866 mmol), and BiPhePhos solution (5.9 × 10 -5 mmol) and Rh(CO)2acac (2 × 10 -5The vessel was purged with H2 / CO 1:1 (4 x 5 bar) and heated at 90 °C with 10 bar syngas pressure for 48 h with vigorous stirring. After cooling and depressurization, the crude was diluted with water (15 ml) and extracted with Et2O (2 x 30 ml). The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated to give a residue (4.66 g) containing 2-((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethan-1-ol (22.9%), 1,2-bis((8,8-dimethyl-1-oxaspiro[4.5]decan-2-yl)oxy)ethane (4%), 2-((1,3-dioxolan-2-yl)methoxy)-8,8-dimethyl-1-oxaspiro[4.5]decane (2.2%), 2-((4,4-dimethyl-1-vinylcyclohexyl)oxy)ethan-1-ol (1.4%), 2-butoxy-8,8-dimethyl-1-oxaspiro[4.5]decane (39.4%), and some secondary unidentified products. The product was isolated by chromatography (Et2O / pentane 1:1) and identified by spectrum.

[0255] 2-Butoxy-8,8-dimethyl-1-oxaspiro[4.5]decane [ka]

[0256] The resulting mixture could be converted to 2-(2-(4,4-dimethylcyclohex-1-en-1-yl)ethyl)-1,3-dioxolane (yield 81%) in the presence of xylene, sulfuric acid (2.5 mol%) and 5 eq of 1,2-ethanediol (azeotropic distillation of water).

[0257] [Example 48] (Hydroformylation of 3,7-dimethyl-1-octen-3-ol) In the autoclave, 3,7-dimethyl-1-octen-3-ol (5.43 g, 34.19 mmol), 1,2-ethanediol (6.53 g, 105.2 mmol), BiPhePhos (3 × 10 -6mmol) and Rh(CO)2acac(10 -6 The vessel was purged with H2 / CO (1:1, 4 x 5 bar), pressurized to 10 bar and then heated at 90 °C under constant pressure and vigorous stirring for 48 h to reach 94% conversion. The crude was diluted with water (15 mL), extracted with Et2O (2 x 30 mL) and the combined organic layers were dried over anhydrous sodium sulfate. The mixture was filtered and concentrated to give a clear liquid residue (7.21 g). GLC analysis of the residue revealed the presence of starting 3,7-dimethyl-1-octen-3-ol (5.9%), 2-((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol (32.6%, 35.3%, 62% yield of both diastereomers), 5,5'-oxybis(2-methyl-2-(4-methylpentyl)tetrahydrofuran) (1.6%, 2% yield), 1,2-bis((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethane (17.6%, 19% yield) and 3,7-dimethyloctan-3-ol (2.9%). The product was isolated by chromatography (Et2O / pentane 1:1) and identified by NMR.

[0258] 2-((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol (diastereomeric mixture): [ka]

[0259] 1,2-Bis((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethane (mixture of diastereomers): [ka]

[0260] [Example 49] (Preparation of Unsaturated Dioxolanes from 2-((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol and 1,2-bis((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethane) In a 10 mL reactor (equipped with a Dean-Stark apparatus and a small column, 2-element Sulzer EX), 1.9 g (8.249 mmol) of 2-((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol obtained in example 48 was stirred with 5 mL of xylene, 4.10 g (65.99 mmol, 8 eq) of 1,2-ethanediol and 18.4 mg (0.188 mmol, 2.3 mol%) (98%) of H2SO4. The mixture was heated to 130 °C-138 °C) and water was collected (Dean-Stark apparatus). After 3 h, complete conversion of 2-((5-methyl-5-(4-methylpentyl)tetrahydrofuran-2-yl)oxy)ethan-1-ol was observed by GC. The mixture was diluted with 10 mL of MTBE and washed with 5 mL of water. The organic phase was then washed with 5 mL of saturated aqueous NaHCO3, once with 5 mL of water, and with 5 mL of saturated aqueous NaCl. After drying over sodium sulfate, the solvent was evaporated under reduced pressure (45° C., 15 mbar). The crude product (2.06 g) was purified by column chromatography (80 g cartridge, 100% cyclohexane to 100% MTBE). 1568 mg (7.385 mmol, 89.5% yield) of a mixture of isomers (ratio 32 / 18 / 27 / 16 / 4) was isolated ((E)-2-(3,7-dimethyloct-3-en-1-yl)-1,3-dioxolane / (Z)-2-(3,7-dimethyloct-3-en-1-yl)-1,3-dioxolane / (E)-2-(3,7-dimethyloct-2-en-1-yl)-1,3-dioxolane / (Z)-2-(3,7-dimethyloct-2-en-1-yl)-1,3-dioxolane / 2-(7-methyl-3-methyleneoctyl)-1,3-dioxolane, ratio 32 / 18 / 27 / 16 / 4).

[0261] (E)-2-(3,7-dimethyloct-3-en-1-yl)-1,3-dioxolane (characteristic signal) [ka]

[0262] GC3.20 min (column DB-1 10 m, 80°C to 320°C (30°C / min) (Z)-2-(3,7-dimethyloct-3-en-1-yl)-1,3-dioxolane (characteristic signal) [ka]

[0263] GC 3.04 min (column DB-1 10 m, 80°C to 320°C (30°C / min) (E)-2-(3,7-dimethyloct-2-en-1-yl)-1,3-dioxolane (characteristic signal) [ka]

[0264] GC 3.16 min (column DB-1 10 m, 80°C to 320°C (30°C / min) (Z)-2-(3,7-dimethyloct-2-en-1-yl)-1,3-dioxolane (characteristic signal) [ka]

[0265] GC3.10 min (column DB-1 10 m, 80°C to 320°C (30°C / min) 2-(7-Methyl-3-methyleneoctyl)-1,3-dioxolane (characteristic signal) [ka]

[0266] GC 3.13 min (column DB-1 10 m, 80°C to 320°C (30°C / min) (E)-2-(3,7-dimethyloct-3-en-1-yl)-1,3-dioxolane / (Z)-2-(3,7-dimethyloct-3-en-1-yl)-1,3-dioxolane / (E)-2-(3,7-dimethyloct-2-en-1-yl)-1,3-dioxolane / (Z)-2-(3,7-dimethyloct-2-en-1-yl)-1,3-dioxolane / 2-(7-methyl-3-methyleneoctyl)-1,3-dioxolane could be deprotected according to the procedure of Example 3 to give unsaturated aldehydes (conversion yield 99%).

[0267] [ka]

[0268] (E)-4,8-Dimethylnon-4-enal / (E)-4,8-Dimethylnon-3-enal / (Z)-4,8-Dimethylnon-4-enal / (Z)-4,8-Dimethylnon-3-enal / 8-Methyl-4-methylenenonanal [ka]

Claims

1. formula 【Chemistry 1】 wherein one dotted line is a carbon-carbon double bond and the other dotted line is a carbon-carbon single bond; m is 0 or 1; R １ is C １－１２ represents a hydrocarbon group, which may optionally contain 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; R ２ is a hydrogen atom or R １ represents a group; or R １ and R ２ Together, C ５－１８ Cycloalkyl group or C ５－１８ cycloalkenyl groups, each of which optionally contains one or more hydroxy groups, C １－１５ Alkyl group, C ２－１５ Alkenyl group, C １－１５ Alkoxy group, C ３－１５ Cycloalkyl group, C ５－１５ Cycloalkenyl group, C １－６ Ester group, COOH group, C ６－１０ Aryl groups and / or C ６－１０ R may be substituted with an aryloxy group; ３ and R ４ are each independently a hydrogen atom or C １－６ Represents an alkyl group; ａ Together, C ２－２０ 1. A process for preparing a compound in the form of any one of the stereoisomers or a mixture thereof of a compound of formula (II) 【Chemistry 2】 [In the formula, R １ , R ２ , R ３ , R ４ and m have the same meaning as defined in formula (I); R ｃ is a hydrogen atom or C １－１２ is a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R ｃ is the formula 【Chemistry 3】 [In the formula, R １ , R ２ , R ３ , R ４ and m have the same meaning as defined in formula (I); n is 0 or 1, R ｄ is C １－１２ is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II ａ ) and the oxygen atom of formula (II) ], with an acid and a polyol or an α-hydroxycarboxylic acid.

2. R ３ and R ４ are each independently a hydrogen atom or C １－３ 2. The method of claim 1, wherein the alkyl group represents a hydrogen atom.

3. 3. The method of claim 1 or 2, wherein m is 0.

4. R １ and R ２ Together, C ５－１２ Cycloalkyl group or C ５－１２ cycloalkenyl groups, each of which optionally has one or two C １－１０ 4. The method of claim 1, wherein the alkyl group is optionally substituted with an alkyl group.

5. R ｃ But, C １－７ is an alkyl group, which may be optionally substituted with one oxo group or one or two hydroxy groups, in particular R ｃ However, (CH ２ ) ｎ 5. The method of claim 1, wherein n is an OH group, where n is 2 or 3 or 4.

6. The compound of formula (I) is represented by the formula 【Chemistry 4】 [In the formula, each R ａ has the same meaning as defined in claim 1, R ５ and R ６ are each independently a hydrogen atom or C １－６ represents an alkyl group], and the compound of formula (II) is in the form of any one of the stereoisomers of the compound of formula 【Chemistry 5】 [In the formula, each R ５ and R ６ The process according to any one of claims 1 to 5, wherein the compound is in the form of any one of the stereoisomers of the compound of formula (III) or a mixture thereof.

7. The acid has a pH of less than 3, in particular the acid is pTsOH, MsOH, TfOH, H ２ SO ４ , HCl, H ３ P.O. ４ , K.H.S.O. ４ , NaHSO ４ , B.F. ３ Et ２ O., B.F. ３ (AcOH) ２ , ZnBr ２ , Fe(OTf) ３、 Fe(OTs) ３ , FeCl ３、 Zn(OTf) ２、 Bi(OTf) ３、 Cu(OTf) ２ , SnCl ４ , Alox acidic, Amberlyst 15, Amberlyst 35, SiO ２ 7. The method of claim 1, wherein the additive is selected from the group consisting of: Wayphos, polyphosphoric acid, zeolites, boric acid, CSA, bentonite, clay.

8. The polyol has the formula HOROH, ２－６ and the α-hydroxycarboxylic acid is a polyol of the formula R'CH(OH)COOH, where R' is a hydrogen atom or １－６ The method according to any one of claims 1 to 7, wherein the α-hydroxycarboxylic acid is an α-hydroxycarboxylic acid having a formula:

9. The compound of formula (I) is reacted with 【Chemistry 6】 [Wherein, dotted line, m, R １ , R ２ , R ３ and R ４ 9. The process according to claim 1, further comprising a step of converting the compound of formula (I) into a compound in the form of any one of the stereoisomers or a mixture thereof,

10. formula 【Chemistry 7】 [In the formula, m is 0 or 1; １ is C １－１２ represents a hydrocarbon group, which may optionally contain 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; R ２ is a hydrogen atom or R １ represents a group; or R １ and R ２ Together, C ５－１８ Cycloalkyl group or C ５－１８ cycloalkenyl groups, each of which optionally contains one or more hydroxy groups, C １－１５ Alkyl group, C ２－１５ Alkenyl group, C １－１５ Alkoxy group, C ３－１５ Cycloalkyl group, C ５－１５ Cycloalkenyl group, C １－６ Ester group, COOH group, C ６－１０ Aryl groups and / or C ６－１０ R may be substituted with an aryloxy group; ３ and R ４ are each independently a hydrogen atom or C １－６ represents an alkyl group; R ｃ is a hydrogen atom, C １－１２ is a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R ｃ is the formula 【Chemistry 8】 [In the formula, R １ , R ２ , R ３ , R ４ and m has the same meaning as defined in formula (II); n is 0 or 1, R ｄ is C １－１２ is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II ａ ) and the oxygen atom of formula (II) ], wherein the compound is a group of formula (II) 【Chemistry 9】 [In the formula, m, R １ , R ２ , R ３ and R ４ has the same meaning as defined in formula (II)] in the presence of a hydroformylation catalyst containing a bidentate phosphorus ligand and an alcohol or a polyol,

11. The process of claim 10, wherein the hydroformylation catalyst is a rhodium catalyst.

12. 12. The process according to claim 10 or 11, wherein said alcohol or polyol is added to the reaction medium of the process defined in claims 10 and 11 in a concentration of at least 1 equivalent relative to the amount of compound of formula (VI), preferably at least 3.4 equivalents relative to the amount of compound of formula (VI).

13. 13. The method of any one of claims 10 to 12, wherein the bidentate phosphorus ligand is a bidentate phosphite ligand.

14. 14. The method of any one of claims 10 to 13, wherein the polyol is a diol.

15. formula 【Chemistry 10】 [In the formula, m is 0 or 1; R １ and R ２ are independent of each other, C １－１２ represents a hydrocarbon group, which may optionally contain 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom; or R １ and R ２ Together, C ５－１８ Cycloalkyl group or C ５－１８ cycloalkenyl groups, each of which optionally contains one or more hydroxy groups, C １－１５ Alkyl group, C ２－１５ Alkenyl group, C １－１５ Alkoxy group, C ３－１５ Cycloalkyl group, C ５－１５ Cycloalkenyl group, C １－６ Ester group, COOH group, C ６－１０ Aryl groups and / or C ６－１０ R may be substituted with an aryloxy group; ３ and R ４ are each independently a hydrogen atom or C １－６ represents an alkyl group; R ｃ is a hydrogen atom, C １－１２ is a hydrocarbon group, which may optionally contain 1 to 5 oxygen atoms, or R ｃ is the formula 【Chemistry 11】 [In the formula, R １ , R ２ , R ３ , R ４ and m has the same meaning as defined in formula (II); n is 0 or 1, R ｄ is C １－１２ is a hydrocarbylene group, which may optionally contain 1 to 5 oxygen atoms, and the hatched lines represent (II ａ ) and the oxygen atom of formula (II) (with the exception of 4-butyl-1-[(5,5-dibutyltetrahydro-2-furanyl)oxy]-2,4-octanediol and 2-[(tetrahydro-5,5-dimethyl-2-furanyl)oxy]ethanol).

Images