Procatalyst and catalyst system for olefin polymerization, and method for olefin (CO)polymerization

Abstract

The present disclosure relates to a procatalyst for olefin polymerization comprising a titanium-containing compound, a magnesium-containing compound, a halogen, and an internal electron donor, wherein the internal electron donor is an alkoxycarbamate compound, and to a method for the preparation of said procatalyst. The present disclosure further relates to a catalyst system for olefin polymerization comprising said procatalyst and a co-catalyst, to a method for the preparation of said catalyst system, and to a method for olefin (co)polymerization with the use of said catalyst system. The present disclosure also relates to use of the alkoxycarbamate compound as an internal electron donor in a catalyst for olefin polymerization.

Description

[0001] PROCATALYST AND CATALYST SYSTEM FOR OLEFIN POLYMERIZATION, AND METHOD FOR OLEFIN (CO)POLYMERIZATION

[0002] TECHNICAL FIELD

[0003] The present disclosure relates to the field of olefin polymerization. In particular, the present disclosure relates to a procatalyst for olefin polymerization comprising a titanium- containing compound, a magnesium-containing compound, a halogen, and an internal electron donor, which is an alkoxycarbamate compound, and to a method for the preparation of said procatalyst. More particularly, the present disclosure relates to a catalyst system containing said procatalyst and a co-catalyst, a method for the preparation of said catalyst system, and a method for olefin (co)polymerization using said catalyst system. The .present disclosure also relates to use of an alkoxycarbamate compound as an internal electron donor in a catalyst for olefin polymerization.

[0004] BACKGROUND ART

[0005] Currently, olefin-based polymers are used in a great variety of applications due to their versatility and clear advantages over other materials and, consequently, the market demand for them is continuously growing. It becomes impossible to imagine the functioning of industries and the household sector without the use of polymers. The discovery and development of catalysts for olefin polymerization was one of the key events in the development of large-scale polymer industry, in particular, polyethylene (PE) and polypropylene (PP) industries, which make up the largest share of the polymer market.

[0006] Despite the fact that modem polymerization catalysts make it possible to produce polymer materials with a wide range of customer properties and improve their performance, research in this area is ongoing. Modern developments in the field of polymers are aimed to a detailed description of the mechanisms of the polymerization process by the action of both traditional catalysts and new catalysts modified using various methods, as well as to providing new effective catalysts that make it possible to obtain polymers and copolymers having new properties, control and predetermine their molecular weight characteristics, structure, etc.

[0007] Ziegler-Natta catalysts are often used in the art to produce olefin-based polymers such as polypropylene. Generally, Ziegler-Natta catalysts contain (i) a procatalyst comprising a transition metal halide (for example, titanium, chromium, or vanadium halide) and an internal electron donor, both supported on a magnesium compound, and also (ii) a cocatalyst, which is, typically, an organoaluminum compound. A preferable class of internal donors widely used in the art is represented by phthalic acid esters. Catalysts using phthalates as internal donors are rather active and can produce polymers with adequate stereoregularity.

[0008] An important advantage of a number of systems used as internal donors consists in their safety for humans. Said property is particularly important for a customer due to use of polymer materials obtained using such systems for everyday purposes. For example, phthalate compounds are not safe for humans and they can accumulate in the body and cause serious health problems. Consequently, strict limitations are imposed on their applications involving human contact with these compounds.

[0009] However, an achievement of appropriate parameters of new internal donors with regard to human safety is not the only and key goal of manufacturers. To ensure the efficiency of internal donors, it is important to provide suitable characteristics of the resulting polymers, in particular, their stereoregularity (degree of isotacticity), and the efficiency of the entire polymerization process.

[0010] The closest to the proposed invention in terms of the structure of the internal donor is the solution disclosed in WO 2013042400 (Toho Titanium (JP), 28.03.2013). The catalyst for olefin polymerization disclosed in this document contains titanium, magnesium, halogen and a compound comprising a carbonate and ether groups. However, this solution does not allow achieving necessary polymer properties, since the obtained polymers are characterized, in particular, by narrow molecular weight distribution (MWD) (the value defined by the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn)) which, according to the examples, ranges from 4.7 to 6.3.

[0011] The aim of the present disclosure is to provide a new phthalate-free procatalyst for olefin (co)polymerization comprising a novel internal electron donor. The other aim of the present disclosure is to provide a new procatalyst having improved catalytic performance, in particular, a new procatalyst with a high catalytic activity that can produce polymers with high isotacticity.

[0012] SUMMARY

[0013] Accordingly, in the first aspect, the invention relates to a procatalyst for olefin polymerization comprising a titanium-containing compound, a magnesium-containing compound, a halogen, and an internal electron donor, which is a compound of Formula (I):

[0014] Formula (I) wherein

[0015] R1is selected from the group consisting of hydrogen, alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14, R2and R3are independently selected from the group consisting of alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14, L is a bridge selected from wherein R4, R5, R6, R7, R8, R9are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl, optionally substituted with one or more same or different substituents R14,

[0016] R10, R11, R12, R13are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl, halogen, optionally substituted with one or more same or different substituents R14, wherein R14is independently selected from the group consisting of alkyl or cycloalkyl, optionally substituted aryl, halogen, and any of R1— R14may be linked together to form one or more saturated or unsaturated carbocyclic rings or saturated or unsaturated heterocyclic rings.

[0017] In the second aspect, the invention relates to a method for the preparation of a procatalyst comprising:

[0018] (a) contacting a magnesium-containing compound with a titanium-containing compound; and

[0019] (b) adding to the mixture obtained in step (a) an internal donor, which is a compound of Formula (I).

[0020] In the third aspect, the invention relates to a catalyst system for olefin polymerization, comprising:

[0021] (a) a procatalyst for olefin polymerization as described above, and

[0022] (b) a co-catalyst.

[0023] In the fourth aspect, the invention relates to a method for the preparation of said catalyst system for olefin polymerization, which method comprises contacting the procatalyst for olefin polymerization described above with a co-catalyst. In the fifth aspect, the invention relates to a method for olefin (co)polymerization, comprising contacting at least one olefin monomer with said catalyst system.

[0024] In the sixth aspect, the invention relates to use of the compound of Formula (I) as an internal electron donor of a catalyst for olefin polymerization.

[0025] DETAILED DESCRIPTION OF THE INVENTION

[0026] Definitions

[0027] In the present disclosure, any reference to the Periodic Table should be regarded as a reference to the variant of the Periodic Table approved and released by IUPAC.

[0028] As used herein, each of the terms "a", "an", and "the" in the singular forms may also refer to and include the plural reference or object, unless specifically otherwise defined or stated therein, or unless the context clearly indicates otherwise.

[0029] Unless stated otherwise, any reference to parts or percentages means parts by weight and percentages by weight.

[0030] As used herein, the expressions "comprise(s)", "comprising" are synonymous with "include(s)", "including", "contain(s)", or "containing" and are inclusive terms that do not exclude or preclude the presence of additional, non-recited herein components, steps, or operations. For avoidance of doubt, all the compositions that are disclosed herein using the term "containing" can include any further additive or excipient, unless otherwise defined. On the contrary, the expression "consisting essentially of is to be understood as excluding any additional, non-recited herein components, steps, or operations from the following list, whereas allowing to contain additionally other items which do not materially affect implementability of the invention. The term "consisting of is to be understood as excluding any component, step, or operation that is not recited or explicitly specified herein. Unless stated otherwise, the term "or" is to be understood as applicable to any individual element recited, as well as to any combination of the recited elements.

[0031] Any numerical range recited herein, includes all values from the lower value to the upper value, in increments of one unit, provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component, or a value of a compositional or a physical property, such as, for example, amount of a blend component, softening temperature, melt index, etc., is between 1 and 100, it is intended that all individual values, such as, 1, 2, 3, etc., and all subranges, such as, 1 to 20, 55 to 70, 97 to 100, etc., are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001 , 0.001, 0.01, or 0.1 , as appropriate. These are only examples of what is specifically intended, and all possible combinations of numerical values between the lowest value and the highest value enumerated, are to be considered to be expressly stated in this application. In other words, any numerical range recited herein includes any value or subrange within the stated range.

[0032] As used herein, the term "composition" refers to a mixture of materials initially constituting the composition and the products that can be formed as a result of their mutual reactions and decomposition reactions of each constituent.

[0033] As used herein, the term "polymer" refers to a macromolecular compound containing repeating structural units referred to as monomers. The term "polymer" includes homopolymers and copolymers.

[0034] As used herein, the term "olefin" refers to alkene.

[0035] As used herein, the terms "olefin-based polymer" or "polyolefin" refer to a polymer containing, in its polymerized form, a majority weight percent of olefin, for example ethylene or propylene, based on the total weight of the polymer. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers.

[0036] As used herein, the term, "ethylene-based polymer" refers to a polymer that comprises a majority weight percent of polymerized ethylene monomer (based on the total weight of polymerizable monomers), and optionally may comprise at least one polymerized comonomer.

[0037] As used herein, the term, "propylene-based polymer" refers to a polymer that comprises a majority weight percent of polymerized propylene monomer (based on the total amount of polymerizable monomers), and optionally may comprise at least one polymerized comonomer.

[0038] As used herein, the term "polypropylene" refers to a polymer consisting of propylene and, optionally, a comonomer.

[0039] As used herein, the term "copolymer" refers to a polymer produced from two or more different monomers. As used herein, the term "monomer" refers to a chemical compound capable of being polymerized.

[0040] As used herein, the term "hydrocarbon" refers to substituents that consist entirely of hydrogen and carbon and can be linear or branched, saturated or unsaturated, cyclic, polycyclic, fused ring or acyclic groups and combinations thereof.

[0041] As used herein, the term "alkyl" refers to an alkyl group that represents a functional group or a side chain consisting of carbon and hydrogen atoms linked by single bonds only. Alkyl group can be linear or branched and can be unsubstituted or substituted. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n -butyl, tert- butyl, isobutyl (or 2-methylpropyl), etc. Alkyl groups can have from 1 to 20 carbon atoms.

[0042] As used herein, the term "substituted alkyl" refers to an alkyl as just described in which one or more (two, three, four, or more) hydrogen atom linked to any carbon atom of the alkyl is replaced by another group such as a halogen, aryl, substituted aryl, alkenyl, substituted alkenyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, haloalkyl, hydroxy, amino, phosphido, alkoxy, thio, nitro, other heteroatom-containing groups, and combinations thereof. Suitable substituted alkyls include, for example, benzyl, trifluoromethyl and the like.

[0043] As used herein, the term "cycloalkyl" refers to a saturated cyclic hydrocarbon group. Cycloalkyl group can be substituted or unsubstituted. Non-limiting examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Cycloalkyl groups can have from 3 to 20 carbon atoms.

[0044] As used herein, the term “heterocycloalkyl” refers to a saturated or unsaturated monocyclic or bicyclic ring which contain 1 or 2 non-carbon atoms. Heterocycloalkyl may contain 3 to 20, preferably 3 to 7, carbon atoms. Non-carbon atoms in the heterocycloalkyl may be selected from N, O, P, B, S or Si. However, heterocycloalkyl groups are not aromatic. Heterocycloalkyl groups containing more than one heteroatom may contain different heteroatoms.

[0045] As used herein, the term “substituted heterocycloalkyf’ refers to heterocycloalkyl in which one or more (two, three, four, or more) hydrogen atom in the ring is replaced by another group such as a halogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, hydroxy, amino, phosphido, alkoxy, thio, nitro, other heteroatom- containing groups, and combinations thereof. As used herein, the term "aryl" refers to an aromatic substituent which can be a single aromatic ring or multiple aromatic rings which can be fused together, linked covalently to each other, or linked to each other via a common linking group such as a methylene group or ethylene group. Aromatic ring(s) can include phenyl, naphthyl, anthracenyl, and biphenyl, among others. The aryls can have from 6 to 20 carbon atoms.

[0046] As used herein, the term "substituted aryl" refers to an aryl group just described in which one or more (two, three, four, or more) hydrogen atoms of the aromatic ring is replaced by another group. As a result, the term "substituted aryl group" also includes alkaryl groups, wherein one or more (two, three, four, or more) hydrogen atoms of the aromatic ring is replaced by alkyl groups, and haloaryl groups, wherein one or more (two, three, four, or more) hydrogen atoms of the aromatic ring is replaced by halogen atom(s).

[0047] As used herein, the term "carbocyclic ring" means a cyclic group consisting of carbon atoms. A carbocyclic ring contains exclusively carbon and hydrogen atoms and does not include atoms of any other type. Carbocyclic rings can be saturated, unsaturated, or aromatic. A carbocyclic ring can have from 3 to 20 carbon atoms.

[0048] As used herein, the term "heterocyclic ring" means a cyclic group consisting of carbon atoms and at least one heteroatom. Suitable heteroatoms may include N, O, P, B, S, or Si. A heterocyclic ring can have from 2 to 20 carbon atoms. Heterocyclic ring can comprise one or more heteroatom(s), in particular, from one to four heteroatoms, for example one, two, three or four hcteroatom(s).

[0049] As used herein, the term "a Ziegler-Natta catalyst" refers to a solid catalytic compound comprising a transition metal and consisting of Ziegler-Natta catalyst particles supported on a metal or metalloid compound (for example, magnesium compound or silicon compound).

[0050] As used herein, the terms "Ziegler-Natta catalytic particles" or "active catalyst particles" refer to transition metal-containing particles comprising a transition metal halide selected from titanium halide, chromium halide, hafnium halide, zirconium halide and vanadium halide.

[0051] As used herein, the terms "internal donor" or "internal electron donor" refer to a compound capable of donating at least one electron pair to at least one metal present in a procatalyst.

[0052] As used herein, the terms "external donor" or "external electron donor" refer to an electron donor compound used as a reactant in olefin polymerization. The electronodonor compound has at least one functional group capable of donating at least one electron pair to a metal atom. External donors arc added to a catalyst system independently of the procatalyst formation.

[0053] As used herein, the term "procatalyst" refers to a component of a catalyst composition, wherein a procatalyst generally comprises a solid carrier containing a transition metal, active catalyst particles, and one or more internal donors.

[0054] As used herein, the term "co-catalyst" is generally known in the art in the field of Ziegler- Natta catalysts and refers to a compound capable of converting a procatalyst into an active polymerization catalyst. Generally, a co-catalyst is an organometallic compound containing metal from Groups 1, 2, 12 or 13 of the Periodic Table. The co-catalyst may include any compounds known in the art as being used as "co-catalysts".

[0055] As used herein, the terms "halide" or "halogen" refer to the halogen selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0056] As used herein, the term "heteroatom" refers to an atom other than carbon or hydrogen. However, as used herein, unless specified otherwise, as described below, the expression "one or more heteroatoms" is to be understood as meaning one or more of F, Cl, Br, I, N, O, P, B, S, or Si. Therefore, the term "heteroatom" also includes halides.

[0057] Unless otherwise specified, indication that any of the groups R are "independently selected from" or "independently represent" means that in case of a molecule containing several of the same groups R, they can have the same meaning or can have a different meaning. For example, if compound R2M has its R independently selected from ethyl or methyl, both R groups can be ethyl, both R groups can be methyl, or one R group can be ethyl and the other R group can be methyl.

[0058] The following is a more detailed description of the present invention. Any embodiment of one aspect of the present invention is to be regarded as applicable to any other aspect of the invention, unless otherwise specified.

[0059] According to one aspect, the invention relates to a procatalyst for olefin polymerization comprising a titanium-containing compound, a magnesium-containing compound, a halogen, and an internal electron donor, which is a compound of Formula (I):

[0060] Formula (I) wherein

[0061] R1is selected from the group consisting of hydrogen, alkyl or cycloalkyl. aryl, optionally substituted with one or more same or different substituents R14, R2and R3are independently selected from the group consisting of alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14, L is a bridge selected from wherein R4, R5, R6, R7, R8, R9are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl, optionally substituted with one or more same or different substituents R14,

[0062] R10, R11, R12, R13are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl, halogen, optionally substituted with one or more same or different substituents R14, wherein R14is independently selected from the group consisting of alkyl or cycloalkyl, optionally substituted aryl, halogen, and any of R1— R14may be linked together to form one or more (two, three, four or more) saturated or unsaturated carbocyclic rings or saturated or unsaturated heterocyclic rings.

[0063] The halogen can be any halogen, for example, fluorine, chlorine, bromine, or iodine.

[0064] In an embodiment of the invention, titanium and the halogen are present in the procatalyst as constituents of a compound containing at least one titanium— halogen bond (for example, titanium halide).

[0065] In an embodiment of the invention, the titanium-containing compound is contained in the procatalyst in the form of the compound having the following formula: wherein R15is C1-C20alkyl group; X is a halogen atom; and n is an integer ranging from 0 to 4. Examples of titanium compounds include, but are not limited to, titanium tetrahalides, such as TiCl4, TiBr4, and Til4; alkoxytitanium trihalides, such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O-«-C4H9)Cl3, Ti(OC2H5)Br3, and Ti(O-z-C4H9)Br3; dialkoxytitanium dihalidcs, such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(O-n-C4II9)2Cl2, and Ti(OC2II5)2Br2; tri alkoxy titanium monohalides, such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O-n-C4H9),Cl, and Ti(OC2H5)3Br; and tetraalkoxytitanium compounds, such as Ti(OCH3)4, Ti(OC2H5)4, and Ti(O-n-GH9)4. In some embodiments, titanium tetrahalides are advantageously used. Titanium compounds can be used as such or in solutions of hydrocarbons or halogenated hydrocarbons.

[0066] In an embodiment of the invention, a magnesium-containing compound suitable for preparation of the solid procatalyst component includes, for example, magnesium compounds wherein magnesium is present in oxidation state +2. In one exemplary embodiment, the magnesium-containing compound is a halogenated magnesium compound. Particular examples of magnesium-containing compounds include, but are not limited to, magnesium halides, such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxymagnesium halides, such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, buthoxymagnesium chloride, and octoxymagnesium chloride; aryloxymagnesium halides, such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; magnesium alkoxides, such as magnesium ethoxide, magnesium isopropoxide, magnesium buthoxidc, magnesium n-octoxide, and magnesium 2-ethylhexoxide; alkyl and aryl magnesium halides such as butyl magnesium chloride, amyl magnesium chloride, isoamyl magnesium chloride, hexyl magnesium chloride, phenyl magnesium chloride, tolylmagnesium chloride, and benzylmagnesium chloride; alkylmagnesium compounds such as dibutylmagnesium, butylethylmagnesium, and butyloctylmagnesium; aryloxymagnesium compounds, such as magnesium phenoxide and magnesium dimethylphenoxide; and magnesium salts of carboxylic acids, such as magnesium laurate, and magnesium stearate.

[0067] According to a preferred embodiment of the invention, halogenated magnesium compounds are used, such as magnesium chloride, alkoxymagnesium chlorides, and aryloxymagnesium chlorides.

[0068] It is known in the art that magnesium-containing carriers and halogenated compounds of titanium used according to the present invention are typical components of Ziegler-Natta catalysts. The procatalyst according to the present invention may comprise any of the magnesium-containing carriers and compounds known in the art. For example, preparation of titanium-magnesium based catalytic compositions supported on various magnesium- containing precursor carriers, such as magnesium halides, (alkyl)magnesium and (aryl)magnesium halides, and (alkoxy)magnesium and (aryloxy)magnesium compounds, used in production of polyolefins, in particular, polypropylenes, can be found, for example, in the following publications: U.S. 4,978,648, WO 96 / 32,427 Al , WO 01 / 23,441 Al, EP 1,283,222 Al, EP 1,222,214 Bl; U.S. 5,077,357; U.S. 5,556,820; U.S. 4,414,132; U.S. 5,106,806; and U.S. 5,077,357, but the method of the invention is not limited to the teachings of these documents.

[0069] The internal electron donor according to the invention is a compound of Formula (I):

[0070] Formula (I) In Formula (I), R1is selected from the group consisting of hydrogen, alkyl, cycloalkyl, and aryl, optionally substituted with one or more (two, three, four, or more) substituents R14that can be same or different.

[0071] In an embodiment, R1is hydrogen.

[0072] In another embodiment, R1is alkyl. Preferably, R1is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6, linear or branched alkyl. In particular, R1can be methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0073] In another embodiment, R1is cycloalkyl. Preferably, R1is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0074] In a further embodiment, R1is aryl. Preferably, R1is C6-C20aryl, more preferably C6-C10aryl, most preferably R1is phenyl. Moreover, said aryl can be substituted with one or more (two, three, four, or more) substituents R14.

[0075] Furthermore, R1can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents RHthat can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular, methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, .sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C1-C10aryl, more preferably C1-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0076] Therefore, R1preferably is hydrogen; alkyl, selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; substituted alkyl, such as benzyl; cycloalkyl, selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl; aryl, selected from the group consisting of phenyl, benzyl, alkylphenyl, such as methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, isopropylphenyl, diisopropylphenyl; haloaryl, such as difluorophenyl, dichlorophenyl, dibromophenyl, methyldifluorophenyl, methyldichlorophenyl, methyldibromophenyl, benzocyclopentyl.

[0077] In Formula (I), R2is selected from the group consisting of alkyl, cycloalkyl, and aryl, optionally substituted with one or more (two, three, four, or more) substituents R14that can be same or different.

[0078] In one embodiment, R2is alkyl. Preferably, R2is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R2can be methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0079] In another embodiment, R2is cycloalkyl. Preferably, R2is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0080] In a further embodiment, R2is aryl. Preferably, R2is C6-C20aryl, more preferably C6-C10aryl, most preferably R2is phenyl. Moreover, said aryl can be substituted with one or more (two, three, four, or more) substituents R14.

[0081] Furthermore, R2can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular, methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that arc preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0082] Therefore, R2preferably is alkyl selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl; aryl selected from the group consisting of phenyl and alkylphenyl, such as methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, isopropylphenyl, diisopropylphenyl.

[0083] In Formula (I), R’ is selected from the group consisting of alkyl, cycloalkyl, and aryl, optionally substituted with one or more (two, three, four, or more) substituents R" that can be same or different.

[0084] In one embodiment, R3is alkyl. Preferably, R3is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R3can be methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0085] In another embodiment, R3is cycloalkyl. Preferably, R3is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0086] In a further embodiment, R3is aryl. Preferably, R3is C6-C20aryl, more preferably C6-C10aryl, most preferably R3is phenyl. Moreover, said aryl can be substituted with one or more (two, three, four, or more) substituents R14. Furthermore, R3can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, .sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-Cl0cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0087] Therefore, R3preferably is alkyl selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl; aryl selected from the group consisting of phenyl and alkylphenyl, such as methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, isopropylphenyl, diisopropylphenyl.

[0088] In an embodiment, R2and R3are the same.

[0089] In Formula (I), L is a bridge selected from:

[0090] In bridge L, R4is selected from the group consisting of hydrogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R14. In an embodiment, R4is hydrogen.

[0091] In another embodiment, R4is alkyl. Preferably, R4is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R4can be methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0092] In another embodiment, R4is cycloalkyl. Preferably, R4is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0093] Furthermore, R4can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C10aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C3-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0094] Therefore, R4preferably is hydrogen; alkyl selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl. In bridge L, R5is selected from the group consisting of hydrogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R14.

[0095] In an embodiment, R5is hydrogen.

[0096] In another embodiment, R5is alkyl. Preferably, R5is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R5can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0097] In another embodiment, R5is cycloalkyl. Preferably, R5is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0098] Furthermore, R5can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, te / 7-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6, alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0099] Therefore, R5preferably is hydrogen; alkyl selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl.

[0100] In bridge L, R6is selected from the group consisting of hydrogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R".

[0101] In an embodiment, R6is hydrogen.

[0102] In another embodiment, R6is alkyl. Preferably, R6is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R6can be methyl, ethyl, n-propyl, isopropyl, H-butyl, isobutyl, .sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0103] In another embodiment, R6is cycloalkyl. Preferably, R6is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0104] Furthermore, R6can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6, linear or branched alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C10cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine. Therefore, R6preferably is hydrogen; alkyl selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl.

[0105] In bridge L, R7is selected from the group consisting of hydrogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R14.

[0106] In an embodiment, R7is hydrogen.

[0107] In another embodiment, R7is alkyl. Preferably, R7is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R7can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl. tertbutyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0108] In another embodiment, R7is cycloalkyl. Preferably, R7is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0109] Furthermore, R7can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-Cl0cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0110] Therefore, R7preferably is hydrogen; alkyl selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl.

[0111] In bridge L, R8is selected from the group consisting of hydrogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R14.

[0112] In an embodiment, R8is hydrogen.

[0113] In another embodiment, R8is alkyl. Preferably, R8is C1-C20linear or branched alkyl, more preferably C1-Cm linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R8can be methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0114] In another embodiment, R8is cycloalkyl. Preferably, R* is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0115] Furthermore, R8can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, Ct-C6linear or branched alkyl, in particular methyl, ethyl, w-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6, alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-Cl0cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0116] Therefore, R8preferably is hydrogen; alkyl selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl.

[0117] In bridge L, R9is selected from the group consisting of hydrogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R14.

[0118] In an embodiment, R9is hydrogen.

[0119] In another embodiment, R9is alkyl. Preferably, R9is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R9can be methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0120] In another embodiment, R9is cycloalkyl. Preferably, R9is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0121] Furthermore, R9can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-Cl(1linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C1-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; 0ptionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0122] Therefore, R9preferably is hydrogen; alkyl selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl.

[0123] In bridge L, R10is selected from the group consisting of hydrogen, halogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R".

[0124] In an embodiment, R10is hydrogen.

[0125] In another embodiment, R10is halogen. Preferably, R10is halogen selected from fluorine, chlorine, bromine or iodine.

[0126] In another embodiment, R10is alkyl. Preferably, R10is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R10can be methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tertbutyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R10.

[0127] In another embodiment, R10is cycloalkyl. Preferably, R10is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0128] Furthermore, R10can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C20alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0129] Therefore, R10preferably is hydrogen; fluorine, chlorine, bromine, or iodine; alkyl selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl.

[0130] In bridge L, R11is selected from the group consisting of hydrogen, halogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R14.

[0131] In an embodiment, R11is hydrogen.

[0132] In another embodiment, R11is halogen. Preferably, R11is halogen selected from fluorine, chlorine, bromine or iodine.

[0133] In another embodiment, R11is alkyl. Preferably, R11is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R" can be methyl, ethyl, w-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0134] In another embodiment, R11is cycloalkyl. Preferably, R11is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0135] Furthermore, R11can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, CrC6linear or branched alkyl, in particular methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C1-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C1-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0136] Therefore, R11preferably is hydrogen; fluorine, chlorine, bromine, or iodine; alkyl selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec- butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl.

[0137] In bridge L, R12is selected from the group consisting of hydrogen, halogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R14.

[0138] In an embodiment, R12is hydrogen.

[0139] In another embodiment, R12is halogen. Preferably, R12is halogen selected from fluorine, chlorine, bromine or iodine.

[0140] In another embodiment, R12is alkyl. Preferably, R12is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R12can be methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0141] In another embodiment, R12is cycloalkyl. Preferably, R12is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0142] Furthermore, R12can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0143] Therefore, R12preferably is hydrogen; fluorine, chlorine, bromine, or iodine; alkyl selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl.

[0144] In bridge L, R13is selected from the group consisting of hydrogen, halogen, alkyl and cycloalkyl, optionally substituted with one or more (two, three, four, or more) same or different substituents R14.

[0145] In an embodiment, R13is hydrogen. In another embodiment, R13is halogen. Preferably, R13is halogen selected from fluorine, chlorine, bromine or iodine.

[0146] In another embodiment, R13is alkyl. Preferably, R13is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R13can be methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, .vec-butyl, tert- butyl, pentyl, or hexyl. Moreover, said alkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0147] In another embodiment, R13is cycloalkyl. Preferably, R13is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl. Moreover, said cycloalkyl can be substituted with one or more (two, three, four, or more) substituents R14.

[0148] Furthermore, R13can be unsubstituted or can be substituted with one or more (two, three, four, or more) substituents R14that can be same or different, wherein each R14is independently selected from the group consisting of: alkyl, such as C1-C20linear or branched alkyl, more preferably C.-Ci# linear or branched alkyl, for example, C-C,, linear or branched alkyl, in particular methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, .sec-butyl, tert-butyl, pentyl, or hexyl; cycloalkyl, such as C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl; optionally substituted aryl, such as C6-C20aryl, more preferably C6-C10aryl, most preferably phenyl, wherein said aryl is optionally substituted with one or more (two, three, four, or more) halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-Cl0alkyl, more preferably C1-C6alkyl, or cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl; halogen, which is preferably fluorine, chlorine, bromine, or iodine.

[0149] Therefore, R13preferably is hydrogen; fluorine, chlorine, bromine, or iodine; alkyl selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl, tert-butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl. R14is independently selected from the group consisting of alkyl, cycloalkyl, optionally substituted aryl and halogen.

[0150] In an embodiment, R14is alkyl. Preferably, R14is C1-C20linear or branched alkyl, more preferably C1-C10linear or branched alkyl, for example, C1-C6linear or branched alkyl. In particular, R" can be methyl, ethyl, n -propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, or hexyl.

[0151] In another embodiment, R14is cycloalkyl. Preferably, R14is C3-C20cycloalkyl, more preferably C3-C10cycloalkyl, still more preferably C3-C6cycloalkyl, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or methylcyclohexyl.

[0152] In a further embodiment, R14is optionally substituted aryl. Preferably. R14is as C6-C20aryl, more preferably C5-C10aryl, most preferably phenyl. Said aryl may be substituted with one or more (two, three, four, or more) substituents selected from the group consisting of halogen atoms that are preferably selected from chlorine, fluorine, bromine, or iodine, alkyl such as C1-C20alkyl, preferably C1-C10alkyl, more preferably C1-C6alkyl, and cycloalkyl such as C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl.

[0153] In a further embodiment, R14is halogen. Preferably, R14is chlorine, fluorine, bromine, or iodine.

[0154] Therefore, R14preferably is alkyl selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, ter / -butyl, pentyl and hexyl; cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl; aryl selected from the group consisting of phenyl, benzyl, alkylphenyl, such as methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, isopropylphenyl, diisopropylphenyl; haloaryl, such as difluorophenyl, dichlorophenyl, dibromophenyl, methyldifluorophenyl, methyldichlorophenyl, methyldibromophenyl, benzocyclopentyl; or halogen selected from the group consisting of fluorine, chlorine, bromine, and iodine.

[0155] In another embodiment, any of R1— R14in Formula (I) and bridge L, which is a part of Formula (I), may be linked together to form one or more (two, three, four, or more) saturated or unsaturated carbocyclic rings or saturated or unsaturated heterocyclic rings. In one embodiment, R1is linked with R6to form heterocyclic ring together with the nitrogen atom to which R1is attached, in particular indoline. In another embodiment, R1is linked with R6to form heterocyclic ring together with the nitrogen atom to which R1is attached, in particular pyrrolidine. In another embodiment, R1is linked with R4or R6to form heterocyclic ring together with the nitrogen atom to which R1is attached, in particular piperidine. In another embodiment, R1is linked with R3to form heterocyclic ring together with the nitrogen and oxygen atoms to which R1and R3are attached respectively, in particular oxazolidine. In another embodiment, R4is linked with R5to form carbocyclic ring, in particular cyclohexane. In another embodiment, R4is linked with R6to form carbocyclic ring, in particular cyclopentane or cyclohexane. In another embodiment, R4is linked with R2to form heterocyclic ring together with the oxygen atom to which R2is attached, in particular tetrahydrofuran. In another embodiment, R1is linked with R2to form heterocyclic ring together with the nitrogen and oxygen atoms to which R1and R2are attached, respectively, in particular morpholine. In another embodiment, R1is linked with R13to form heterocyclic ring together with the nitrogen atom to which R1is attached, in particular tetrahydroquinoline. In another embodiment, R1is linked with R8to form heterocyclic ring together with the nitrogen atom to which R1is attached, in particular piperidine. In one embodiment, said carbocyclic ring or heterocyclic ring contains from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms. The heteroatom in the said heterocyclic ring can be selected from the group consisting of oxygen, nitrogen, sulfur, boron, silicon, phosphorus and halogen. A heterocyclic ring may include one or more heteroatoms, in particular from one to four heteroatoms, for example, one, two, three, or four heteroatoms.

[0156] Specific examples of compounds of Formula (I) used as an internal donor are the following: methyl (2-methoxyethyl)carbamate, ethyl (2-methoxyethyl)carbamate, ethyl ethyl(2-methoxyethyl)carbamate, ethyl isobutyl(2-methoxyethyl)carbamate, ethyl benzyl(2-methoxyethyl)carbamate, ethyl phenyl(2-methoxyethyl)carbamate, ethyl isopropyl(2-methoxyethyl)carbamate, ethyl ethyl(3-methoxypropyl)carbamate, ethyl ethyl(2-methoxyphenyl)carbamate, ethyl (2-methoxyethyl)(2-methylcyclohexyl)carbamate, 3-((tetrahydrofuran-2-yl)methyl)oxazolidin-2-one, ethyl ethyl((tetrahydrofuran-2- yl)methyl)carbamate, ethyl (2-isobutyl-2-(methoxymethyl)-4- methylpentyl)(methyl)carbamate, ethyl (4-methoxypentan-2-yl)(methyl)carbamate, ethyl 2-(2-methoxyethyl)piperidine- 1 -carboxylate, ethyl 2-(methoxymethyl)piperidine- 1 - carboxylate, ethyl 3-(methoxymethyl)piperidine- 1 -carboxylate, ethyl 3-methoxypiperidine- 1 -carboxylate, ethyl 3-methoxypyrrolidine-l -carboxylate, ethyl 4-methoxypiperidine-l- carboxylate, ethyl isopropyl(2-methoxycyclohexyl)carbamate, ethyl isopropyl(2- methoxycyclopentyl)carbamate, ethyl (2,6-diethylphenyl)(2-methoxyethyl)carbamate, ethyl (2,6-dibrom-4-methyl)(2-methoxyethyl)carbamate, ethyl ethyl(2-methoxy-2- methylethyl)carbamate, ethyl ethyl(2-rnethoxy-2,2-dimethylethyl)carbamate, ethyl ethyl(2- methoxy-2-(2-methylphenyl)ethyl)carbamate, ethyl ethyl(2-methoxy-2-(2- methylbenzyl)ethyl)carbamate, ethyl ethyl(2-methoxy- 1 -(2-methylbenzyl)ethyl)carbamate, ethyl ethyl(2-methoxy-1-(2-methylphenyl)ethyl)carbamate, ethyl ethyl(2-methoxy-l,l- dimethylethyl)carbamate, ethyl ethyl(2-(2-methylphenoxy)ethyl)carbamate, 2-(2- methylphenyl)ethylethyl(2-(2-methylphenoxy)ethyl)carbamate, phenyl ethyl(2- methoxyethyl)carbamate, (2-methyl-4-chlorophenyl)ethyl(2-methoxyethyl)carbamate, ethyl methyl(2-methoxyphenyl)carbamate, ethyl ethyl((1- methoxycyclohexyl)methyl)carbamate, ethyl 4-morpholinecarboxylate, ethyl (2- methoxyethyl)(o-tolyl)carbamate, ethyl ethyl(1-methoxybutan-2-yl)carbamate, isobutyl ethyl(2-methoxyethyl)carbamate, ethyl (S)-2-(methoxymethyl)pyrrolidine- 1 -carboxylate, ethyl isopropyl(2-methoxypropyl)carbamate, (S)-2-(methoxymethyl)indoline- 1 - carboxylate, 3-(2-methoxyethyl)oxazolidin-2-one, 3-(2-methoxyethyl)- 1 ,3-oxazinan-2-one, and ethyl 8-methoxy-3,4-dihydroquinoline-l(2Zf)-carboxylate.

[0157] Compound of Formula (I) can be obtained, in particular, by the following four routes.

[0158] 1. Compound of Formula (I) can be obtained by reacting a substituted amine with chloroformate ester in a solvent and a base at room temperature followed by reacting the resulting carbamate with a reagent containing R1in the presence of a strong base, and optionally a palladium based, copper based, or another transition metal based catalyst: wherein X = Cl, Br, I, OSO2Me, OSO2-p-To or OSO2CF3.

[0159] 2. Compound of Formula (I) can be obtained by reacting an amine containing R1with a chloroformate ester in the presence of a base and a solvent at room temperature:

[0160]

[0161] 3. Compound of Formula (I) can be obtained by reacting carbamates containing substituents R1and R3with halogenated ether in the presence of a base and a solvent: wherein

[0162] 4. Compound of Formula (I) can be obtained by reacting a substituted amine containing two methyl groups with chloroformate ester in a solvent medium under heating:

[0163] Non-limiting examples of suitable compounds that can be used as bases in the present invention include potassium carbonate, sodium carbonate, sodium hydrogencarbonate, cesium carbonate, sodium hydride, potassium hydride, triethylamine, diisopropylethylamine, etc.

[0164] Non-limiting examples of suitable solvents include dichloromethane, acetonitrile, dimethylformamide, tetrahydrofuran, 1 ,4-dioxane, etc.

[0165] According to one embodiment of the invention, provided is a procatalyst for olefin polymerization that contains a titanium-containing compound, a magnesium-containing compound, a halogen, and an internal electron donor, which is a compound of Formula (I).

[0166] According to a further aspect of the invention, provided is a method for the preparation of a procatalyst for olefin polymerization that contains a titanium-containing compound, a magnesium-containing compound, a halogen, and an internal electron donor, which is a compound of Formula (I).

[0167] In an embodiment, said method comprises the following steps: (a) contacting a magnesium-containing compound, preferably MgCl2, with a titanium-containing compound, preferably TiCl4; and (b) adding an internal donor, which is a compound of Formula (I), to the resulting mixture. In an embodiment, the magnesium-containing compound, which is to be combined with TiCl4in step (a), is present in a mixture with phthalic anhydride, epichlorhydrin, tributylphosphate, and toluene, and said mixture is chilled to -30°C prior to combining with TiCl4. In a further embodiment, combining MgCl2with TiCl4in step (a) is performed by dropwise addition of TiCl4while maintaining the temperature of the mixture below -25°C. In a further embodiment, the mixture of step (a) is heated to 85°C prior to addition of an internal donor. In an embodiment, addition of an internal donor to the mixture obtained in step (a) is performed as a two-stage operation. A suspension obtained in step (b) is filtered, washed, and dried to yield the target particulate procatalyst for olefin polymerization.

[0168] According to a further aspect of the invention, provided is a catalyst system for olefin polymerization comprising:

[0169] (a) a procatalyst for olefin polymerization as described above, and

[0170] (b) a co-catalyst.

[0171] The catalyst system according to the present invention may comprise a co-catalyst. The co- catalyst according to the invention is usually an organometallic compound, containing a metal of Group 1, 2, 12, or 13 of the Periodic Table. The co-catalyst of the invention can be any compound, which is known to be used as a "co-catalyst" in the art.

[0172] The co-catalyst can be at least one organoaluminum compound. According to the invention, any compound having at least one aluminum-carbon bond in its molecule can be used. Examples of organoaluminum compounds include molecules of formula AlR19mX-m, where R19is independently selected from hydrocarbon groups generally having from 1 to 20 carbon atoms, X is a hydrogen or halogen atom, and m is greater than 0 and equal to or less than 3.

[0173] Specific examples of organoaluminum compounds suitable for use as the co-catalyst include, but not limited to, various trialkylaluminums, such as triethylaluminum, tri isobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum; various trialkenylaluminums, such as triisoprenylaluminum; dialkylaluminum halides, such as diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide; alkylaluminum sesquihalides, such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromidc; dialkylaluminum hydrides, such as diethylaluminum hydride, and dibutylaluminum hydride; and other partly hydrogenated alkylaluminums, such as ethylaluminum dihydridc, and propylaluminum dihydride.

[0174] Organoaluminum compound is present in the catalyst system in such an amount that molar ratio of aluminum to titanium (present in the procatalyst) is from about 0.1 to about 1500. In another embodiment, the molar ratio of aluminum to titanium in the catalyst system is from about 5 to about 1000. In another embodiment, the molar ratio of aluminum to titanium in the catalyst system is from about 10 to about 700. In a further embodiment, the molar ratio of aluminum to titanium in the catalyst system is from about 25 to about 400.

[0175] In an embodiment, the catalyst system for olefin polymerization further comprises an external electron donor.

[0176] The external electron donor used in the catalyst system can include any compounds known as external electron donors in the art. Examples of preferred external donors include silicon compounds, ethers, esters, amines, and heterocyclic compounds.

[0177] Another class of preferred external donor compounds is that of silicon compounds of formula wherein a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R16R17, and R18are radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, c is 2, at least one of R16and R17is selected from branched alkyl, cycloalkyl, or aryl groups with 3-10 carbon atoms optionally containing heteroatoms and R18is a C1-C10alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t- butyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2- ethylpiperidinyl)hexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2- ethylpiperidinyl)dimethoxysilane, methyl(3 ,3 ,3-trifluoro-n-propyl)dimethoxysilane, N,N- diethylaminotriethoxysilane. Moreover, also preferred are the silicon compounds in which a is 0, c is 3, R17is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R18is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, and hexyltrimethoxysilane.

[0178] The external electron donor is used in such an amount to give a molar ratio between the co- catalyst, which is preferably an organoaluminium compound, and said external electron donor of from 0.1 to 600, preferably from 1 to 300, and more preferably from 3 to 100.

[0179] In another aspect of the invention, provided is a method for the preparation of a catalyst system for olefin polymerization, the method comprising contacting the procatalyst, as described above, with the co-catalyst, as described above. In one embodiment, the procatalyst is contacted with the co-catalyst in the presence of the external electron donor, as described above. The procatalyst is contacted with the co-catalyst in such amounts to give a molar ratio of aluminum to titanium in the catalyst system of from about 0.1 to about 1500, preferably from about 5 to about 1000, more preferably from about 10 to about 700, still more preferably from about 25 to about 400. When the external electron donor is present, it is used in such an amount to give a molar ratio between the co-catalyst and said external electron donor of from 0.1 to 600, preferably from 1 to 300, and more preferably from 3 to 100. The conditions under which the procatalyst is contacted with the co-catalyst and, optionally, external electron donor include temperatures from 20 to 120°C, preferably from 40 to 80°C, and pressure from 0.5 to 10 MPa, preferably from 1 to 5 MPa, for example from 1.5 to 4 MPa. Furthermore, the pre-contact of the procatalyst with the co- catalyst and optional external electron donor is carried out at a temperature of about 10°C.

[0180] In another aspect of the invention, provided is a method for olefin (co)polymerization, the method comprising contacting at least one olefin monomer with the catalyst system described above. In one embodiment of the invention, the olefins are alpha-olefins. Preferably, the olefins contain from 2 to 40 carbon atoms, more preferably from 2 to 12 carbon atoms. In particular, the olefins can be selected from ethylene, propylene, butene-1, 4-methyl-l -pentene, hexene- 1 and octene- 1.

[0181] The method for olefin (co)polymerization can be carried out in accordance with any polymerization technique known in the art, for example, slurry polymerization in inert hydrocarbon diluent, or bulk polymerization using liquid monomer (for example, propylene) as reaction medium. Furthermore, the method for olefin (co)polymerization can be carried out in gas phase in a fluidized bed reactor or in a stirred bed reactor. According to the invention, the (co)polymerization temperatures generally range from 20 to 120°C, preferably from 40 to 80°C. In case of gas phase (co)polymerization, the operational pressures generally range from 0.5 to 10 MPa, preferably from 1 to 5 MPa. In case of bulk (co)polymerization, the operational pressure usually ranges from 1 to 6 MPa, preferably from 1.5 to 4 MPa. The resulting polymer molecular weight can be controlled by means of adding hydrogen or other compounds known to be used as chain-transfer agents.

[0182] The (co)polymerization process may include a pre-polymerization step. Said step can be carried out in any way known in the art. In one embodiment, pre-polymerization includes contacting a small amount of the olefin with the catalyst system after the procatalyst has been contacted with the co-catalyst and the external electron donor. Then, the resulting preactivated catalyst stream is introduced into the polymerization reaction zone and contacted with the remainder of the olefin monomer to be polymerized, and optionally one or more of the external electron donors. The pre-polymerization step is preferably carried out at a temperature of from 15 to 20°C. Pre-polymerization results in the procatalyst being combined with the co-catalyst and the external electron donor, the combination being dispersed in a matrix of the formant polymer. Optionally, additional quantities of the external electron donor may be added.

[0183] In another aspect of the invention, provided is a use of the compound of Formula (I) as an internal electron donor of a catalyst for olefin polymerization.

[0184] EXAMPLES

[0185] Determination of the content of titanium in the samples of Ziegler-Natta catalysts was conducted using inductively coupled plasma atomic emission spectrometer Agilent 5110. Determination of the content of the internal donors in the catalysts was conducted using 'H NMR with internal standard (1,2,4,5-tetramethylbenzene) in a mixture of CD2Cl2-CD,OD or in a mixture of CDCl3-CD3OD.1H and13C NMR spectra were recorded on Bruker AVANCE (400 MHz) or Agilent Technologies 400-MR (400 MHz) NMR spectrometers. Determination of the content of xylene solubles in the polymer samples was conducted according to ASTM D 5492-17. Determination of Molecular Weight Distribution (MWD) and polydispersity index of polypropylene samples was conducted by Gel Permeation Chromatography (GPC) on Agilent PL-GPC 220 system in accordance with ISO 16014- 4:2012 "Plastics — Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography — Part 4: High-temperature method". Dissolution and measurement temperature was 150°C, solvent was 1,2,4- trichlorobenzene.

[0186] Examples 1-29. Synthesis of internal donors. Comparative examples C30 and C31.

[0187] Example 1. Synthesis of ethyl (2-methoxyethyI)carbamate (D53)

[0188] To a solution of 2-methoxyethan-1-amine (5.00 g, 66.6 mmol) and triethylamine (13.8 ml, 10.1 g, 100 mmol) in dichloromethane (70 ml) a solution of ethyl chloroformate (7.00 ml, 7.95 g, 73.2 mmol) in dichloromethane (20 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (300 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 7.73 g (79%) of the product as a clear colorless liquid, b.p. 66°C / 1 mbar.

[0189] 1H NMR (400 MHz, CDCl3): δ 5.14 (br. s, 1 H), 4.07 (q, J= 7.0 Hz, 2 H), 3.46 - 3.39 (m, 2 H), 3.37 - 3.26 (m, 2 H), 3.32 (s, 3 H), 1.20 (t, .7 7.1 Hz, 3 H).

[0190] 13C NMR (101 MHz, CDCl3): δ 156.6, 71.4, 60.6, 58.6, 40.6, 14.5.

[0191] Example 2. Synthesis of ethyl ethyl(2-methoxyethyl)carbamate (D59)

[0192] To a suspension of NaH (prepared from 1.05 g of 60% suspension in mineral oil, 26.2 mmol, washed with hexane) in a mixture of THF (80 ml) and DMF (40 ml) a solution of ethyl (2-methoxyethyl)carbamate (3.50 g, 23.8 mmol) in THF (40 ml) was added dropwise at 0°C, followed by ethyl iodide (2.87 ml, 5.57 g, 35.7 mmol) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (400 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic extracts were washed with water (3 x 100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled on a Kugelrohr apparatus at 50°C / 0.12 mbar to give 3.73 g (90%) of the product as a clear colorless liquid.

[0193] 1H NMR (400 MHz, CDCl3): δ 4.06 (q, 7.1 Hz, 2 H), 3.51 - 3.18 (m, 6 H), 3.27 (s, 3

[0194] H), 1.18 (t, J= 7.1 Hz, 3 H), 1.04 (t, J= 7.0 Hz, 3 H).

[0195] 13C NMR (101 MHz, CDCl3): δ 71.1, 60.8, 58.6, 46.6, 45.9, 42.8, 42.7, 14.5, 13.5, 13.0.

[0196] Example 3. Synthesis of ethyl isobutyl(2-methoxyethyl)carbamate (D67)

[0197] To a suspension of NaH (prepared from 1.49 g of 60% suspension in mineral oil, 37.4 mmol, washed with hexane) in a mixture of THF (100 ml) and DMF (50 ml) a solution of ethyl (2-methoxyethyl)carbamate (5.00 g, 34.0 mmol) in THF (20 ml) was added dropwise at 0°C, followed by a solution of isobutyl bromide (5.54 ml, 6.98 g, 51.0 mmol) in THF (20 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (400 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic extracts were washed with water (3 x 100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 2 / 1, v / v) to give 1.84 g (31%) of the product as a clear colorless liquid.

[0198] 1H NMR (400 MHz, CDCl3): δ 4.10 (q, J = 7.0 Hz, 2 H), 3.55 - 3.33 (m, 4 H), 3.32 (s, 3 H), 3.14 - 3.03 (m, 2 H), 1.98 - 1.81 (m, 1 H), 1.23 (t, J= 7.1 Hz, 3 H), 0.92 - 0.78 (m, 6 H).13C NMR (101 MHz, CDCl3): δ 156.7, 156.5, 71.0, 70.8, 60.9, 58.8, 55.5, 55.2, 47.3, 46.8, 27.5, 27.2, 19.9, 14.6.

[0199] Example 4. Synthesis of ethyl benzyl(2-methoxyethyl)carbamate (D68)

[0200] To a suspension of NaH (prepared from 1.49 g of 60% suspension in mineral oil, 37.4 mmol, washed with hexane) in a mixture of THF (100 ml) and DMF (50 ml) a solution of ethyl (2-methoxyethyl)carbamate (5.00 g, 34.0 mmol) in THF (20 ml) was added dropwise at 0°C, followed by a solution of benzyl iodide (11.1 g, 51.0 mmol) in THF (20 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (400 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic extracts were washed with water (3 x 100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 7.42 g (92%) of the product as a yellowish liquid.

[0201] 1H NMR (400 MHz, CDCl3): δ 7.41 - 7.16 (m, 5 H), 4.57 (s, 2 H), 4.27 - 4.10 (m, 2 H), 3.58 - 3.33 (m, 4 H), 3.31 (s, 3 H), 1.38 - 1.11 (m, 3 H).

[0202] 13C NMR (101 MHz, CDCl3): δ 156.5, 138.1, 128.4, 127.8, 127.1, 71.0, 61.3, 58.7, 51.1, 46.3, 45.5, 14.6.

[0203] Example 5. Synthesis of ethyl phenyl(2-methoxyethyl)carbamate (D73)

[0204] A mixture of ethyl (2-methoxyethyl)carbamate (5.00 g, 34.0 mmol), bromobenzene (8.00 g, 51.0 mmol), Cs2CO3(22.1 g, 67.9 mmol), Pd(dba)2(0.98 g, 1.70 mmol), XPhos (1.62 g, 3.40 mmol), molecular sieves 3 Å (6.80 g) and toluene (250 ml) was stirred for 12 h at 1 10°C. The resulting mixture was cooled and filtered through a thin pad of Celite 503, which was then washed with an additional amount of dichloromethane (2 x 100 ml). The filtrate was washed with water (100 ml), dried over Na2SO4and the solvents were removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = from 10 / 1 to 5 / 1, v / v) to give 6.63 g (87%) of the product as an orange liquid.

[0205] 1H NMR (400 MHz, CDCl3): δ 7.37 - 7.31 (m, 2 H), 7.27 - 7.19 (m, 3 H), 4.15 (q, J = 7.0 Hz, 2 H), 3.83 (t, J = 6.0 Hz, 2 H), 3.51 (t, J= 6.0 Hz, 2 H), 3.31 (s, 3 H), 1.28 - 1.1 1 (m, 3 H).

[0206] 13C NMR (101 MHz, CDCl3): δ 155.5, 141.9, 128.7, 127.2, 126.3, 69.7, 61.4, 58.5, 49.5, 14.4.

[0207] Example 6. Synthesis of ethyl isopropyl(2-methoxyethyl)carbamate (D74)

[0208] To a suspension of NaH (prepared from 4.48 g of 60% suspension in mineral oil, 112 mmol, washed with hexane) in a mixture of THF (300 ml) and DMF (150 ml) a solution of ethyl (2-methoxyethyl)carbamate (15.0 g, 102 mmol) in THF (50 ml) was added dropwise at 0°C, followed by isopropyl iodide (26.0 g, 153 mmol) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (600 ml) and extracted with dichloromethane (3 x 150 ml). The combined organic extracts were washed with water (3 x 200 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 5 / 1, v / v) to give 1 .75 g (9%) of the product as an orange liquid.

[0209] 1H NMR (400 MHz, CDCl3): δ 4.36 - 4.02 (br. s. 1 H), 4.10 (q, J = 7.1 Hz, 2 H), 3.43 (m, 2 H), 3.32 (s, 3 H), 3.26 (br. s., 2 H), 1.23 (t, J= 7.1 Hz, 3 H), 1.11 (d, J= 6.8 Hz, 6 H).13C NMR (101 MHz, CDCl3): δ 156.1, 71.5 (br. s.), 60.9, 58.7, 47.7, 41.6 (br. s.), 20.6 (br. s.), 14.6.

[0210] Example 7. Synthesis of ethyl ethyl(3-methoxypropyl)carbamate (D75)

[0211] 1. Ethyl (3-methoxypropyl)carbamate

[0212] To a solution of 3 -methoxypropan-1-amine (30.0 g, 337 mmol) and triethylamine (70.5 ml,

[0213] 51.2 g, 506 mmol) in dichloromethane (400 ml) a solution of ethyl chloroformate (35.4 ml,

[0214] 40.2 g, 371 mmol) in dichloromethane (100 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (500 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 100 ml). The combined organic extracts were washed with water (200 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 45.7 g (84%) of the product as a clear colorless liquid, b.p. 80-85°C / l mbar.

[0215] 1H NMR (400 MHz, CDCl3): δ 5.13 (br. s., 1 H), 4.04 (q, J = 7.1 Hz, 2 H), 3.41 - 3.36 (m, 2 H), 3.26 (s, 3 H), 3.20 (t, J= 6.5 Hz, 2 H), 1.74 - 1.66 (m, 2 H), 1.17 (t, J = 7.1 Hz, 3 H).

[0216] 13C NMR (101 MHz, CDCl3): δ 156.6, 70.8, 60.4, 58.5, 38.9, 29.5, 14.5.

[0217] 2. Ethyl ethyl(3-methoxypropyl)carbamate (D75)

[0218] To a suspension of NaH (prepared from 2.73 g of 60% suspension in mineral oil, 68.2 mmol, washed with hexane) in a mixture of THF (200 ml) and DMF (100 ml) a solution of ethyl (3-methoxypropyl)carbamate (10.0 g, 62.0 mmol) in THF (50 ml) was added dropwise at 0°C, followed by a solution of ethyl iodide (7.48 ml, 14.5 g, 93.1 mmol) in THF (50 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (400 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic extracts were washed with water (3 x 100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 9.09 g (77%) of the product as a clear colorless liquid, b.p. 65-67°C / 2 mbar.

[0219] 1H NMR (400 MHz, CDCl3): δ 4.06 (q, J= 7.1 Hz, 2 H), 3.32 (I, J= 6.1 Hz, 2 H). 3.26 (s, 3 H), 3.25 - 3.12 (m, 4 H), 1.81 - 1.65 (m, 2 H), 1.19 (t, J= 7.1 Hz, 3 H), 1.04 (t, J = 7.1 Hz, 3 H).

[0220] 13C NMR (101 MHz, CDCl3): δ 156.1, 70.0 (br. s.), 60.7, 58.4, 44.2 (br. s.), 43.4 (br. s.), 42.1 (br. s.), 41.9 (br. s.), 28.8 (br. s.), 28.4 (br. s.). 14.5, 13.7 (br. s.), 13.1 (br. s.).

[0221] Example 8. Synthesis of ethyl ethyl(2-methoxyphenyl)carbamate (D76)

[0222] 1. Ethyl (2-methoxyphenyl)carbamate

[0223] To a solution of 2-methoxyaniline (13.7 ml, 15.0 g, 122 mmol) and triethylamine (25.5 ml,

[0224] 18.5 g, 183 mmol) in dichloromethane (200 ml) a solution of ethyl chloroformate (12.8 ml,

[0225] 14.5 g, 134 mmol) in dichloromethane (20 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (300 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 5.23 g (22%) of the product as a clear colorless oil, b.p. 72°C / 1 mbar.

[0226] 1H NMR (400 MHz, CDCl3): δ 7.79 (br. s., 1 H), 7.24 - 7.19 (m, 1 H), 7.17 (m, 1 H), 7.08 - 6.99 (m, 1 H), 6.52 (br. s., 1 H), 4.24 (q, J= 1A Hz, 2 H), 2.26 (s, 3 H), 1.33 (t, J= 7.2 Hz, 3 H).

[0227] 13C NMR (101 MHz, CDCl3): δ 153.9, 135.8, 130.2, 126.7, 123.9, 121.1 (br. s.), 61.1, 17.5, 14.4. 2. Ethyl ethyl(2-methoxyphenyl)carbamate (D76)

[0228] To a suspension of NaH (prepared from 1.18 g of 60% suspension in mineral oil, 29.0 mmol, washed with hexane) in a mixture of THF (100 ml) and DMF (50 ml) a solution of ethyl (2-methoxyphenyl)carbamate (5.23 g, 27.0 mmol) in THF (20 ml) was added dropwise at 0°C, followed by a solution of ethyl iodide (3.23 ml, 6.27 g, 40.0 mmol) in THF (20 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (400 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic extracts were washed with water (3 x 100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 4.35 g (72%) of the product as a clear colorless liquid, b.p. 84-86°C / 2 mbar.

[0229] 1H NMR (400 MHz, CDCl3): δ 7.29 - 7.00 (m, 4 H), 4.28 - 3.98 (m, 2 H), 3.87 - 3.65 (m, 1 H), 3.59 - 3.37 (m, 1 H), 2.21 (s, 3 H), 1.42 - 1.06 (m, 6 H).

[0230] 13C NMR (101 MHz, CDCl3): δ 155.3, 140.1, 135.9, 130.8, 130.6, 128.2, 127.2, 126.5, 126.3, 61.1 , 44.8, 44.6, 17.5, 14.5, 13.7, 13.1.

[0231] Example 9. Synthesis of ethyl (2-methoxyethyl)(2-methylcycIohexyl)carbamate (D82)

[0232] I . N-(2-methoxyethyl)-2-methylcyclohexan- 1 -amine

[0233] A mixture of 2-methylcyclohexan- 1 -amine (mixture of cis and trans isomers) (10.0 ml, 8.56 g, 75.8 mmol), l-bromo-2-methoxy ethane (7.10 ml, 10.53 g, 85.8 mmol), K2CO3(21.0 g, 252 mmol) and acetonitrile (100 ml) was stirred for 3 days at room temperature and then poured into water (200 ml). The crude product was extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled on a Kugelrohr apparatus at 50°C / 0.12 mbar to give 6.00 g (46%) of the product (mixture of isomers) as a red oil.

[0234] 1H NMR (400 MHz, CDCl3) for the mixture of isomers: d 3.53 - 3.38 (m, 2 H), 3.38 - 3.27 (m, 3 H), 2.87 - 2.51 (m, 2 H), 2.03 - 1.85 (m, 1 H), 1.84 - 1.54 (m, 3 H), 1.54 - 1.35 (m, 2 H), 1.34 - 1.15 (m, 3 H), 1.14 - 0.84 (m, 5 H).

[0235] 13C NMR (101 MHz, CDCl3) for a major isomer: S 72.3, 62.9, 58.7, 46.3, 37.7, 34.5, 32.1, 26.0, 25.5, 19.2.

[0236] 2. Ethyl (2-methoxyethyl)(2-methylcyclohexyl)carbamate (D82)

[0237] To a solution of N-(2-methoxyethyl)-2-methylcyclohexan-l -amine (2.00 g, 11.7 mmol) and triethylamine (1.80 ml, 1.30 g, 12.9 mmol) in dichloromethane (25 ml) a solution of ethyl chloroformate (1.11 ml, 1.27 g, 11.7 mmol) in dichloromethane (10 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (300 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: dichloromethane / ethyl acetate = 4 / 1, v / v) to give 2.00 g (71%) of the product (mixture of isomers) as a orange oil.

[0238] 1H NMR (400 MHz, CDCl3) for the mixture of isomers: δ 4.20 - 4.01 (m, 2 H), 3.56 - 3.03 (m, 7 H), 2.02 - 0.72 (m, 16 H).

[0239] 13C NMR (101 MHz, CDCl3) for the mixture of isomers: 6 156.8, 71.5, 70.9, 60.9, 58.7,

[0240] 58.7, 58.1, 35.5, 35.1, 34.8, 34.7, 32.5, 31.4, 31.1, 26.5, 26.1, 26.0, 25.8, 25.6, 25.4, 19.6,

[0241] 18.8, 18.7, 14.6, 12.7.

[0242] Example 10. Synthesis of 3-((tetrahydrofuran-2-yl)methyl)oxazolidin-2-one (D86)

[0243] To a suspension of NaH (prepared from 2.42 g of 60% suspension in mineral oil, 60.3 mmol, washed with hexane) in DMF (60 ml) a solution of oxazolidin-2-one (5.00 g, 57.5 mmol) in DMF (10 ml) was added dropwise at 0°C, followed by a solution of 2- (chloromethyl)tetrahydrofuran (8.11 ml, 9.00 g, 74.7 mmol) in DMF (10 ml) dropwise at room temperature. The mixture was stirred for 12 h at 80°C and then quenched with methanol (5 ml). Further, DMF was removed on a Kugelrohr apparatus at 40°C / 0.20 mbar. The residue was diluted with dichloromethane (50 ml) and filtered through a thin pad of Celite 503, which was then washed with additional amount of dichloromethane (2 x 50 ml). The filtrate was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: dichloromethane / methanol = 30 / 1 , v / v) to give 3.55 g (36%) of the product as a clear colorless liquid.

[0244] 1H NMR (400 MHz, CDCl3): δ 4.26 (t, J= 8.1 Hz, 2 H), 3.99 (dq, J = 3.2, 7.2 Hz, 1 H), 3.85 - 3.65 (m, 3 H), 3.60 (q, J = 8.4 Hz, 1 H), 3.41 (dd, J= 3.2, 14.4 Hz, 1 H), 3.11 (dd, J = 7.5, 14.3 Hz, 1 H), 2.01 - 1.76 (m, 3 H), 1.60 - 1.44 (m, 1 H).

[0245] 13C NMR (101 MHz, CDCl3): δ 158.7, 77.8, 68.0, 61.9, 48.2, 45.9, 28.7, 25.5.

[0246] Example 11. Synthesis of ethyl (2, 6-diethylphenyl)(2-methoxy ethylcarbamate (D89)

[0247] 1. Ethyl (2,6-dicthylphenyl)carbamate

[0248] To a mixture of 2,6-diethylaniline (5.00 g, 33.6 mmol) and K2CO3(9.00 g, 61.0 mmol) in chloroform (60 ml) a solution of ethyl chloroformate (2.90 ml, 3.31 g, 30.5 mmol) in chloroform (10 ml) was added dropwise at room temperature. The mixture was stirred for 12 h at 60°C and then was poured into water (150 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvents were removed under reduced pressure. The residue was distilled on a Kugelrohr apparatus at 90°C / 0.08 mbar to give 4.08 g (55%) of the product as a red oil.

[0249] 1H NMR (400 MHz, CDCl3): δ 7.26 - 7.19 (m, 1 H), 7.13 (d, .7 = 7.6 Hz, 2 H), 5.98 (br. s„ 1 H), 4.21 (br. s., 2 H), 2.65 (q, J= 7.6 Hz, 4 H), 1.41 - 1.23 (m, 3 H), 1.21 (t, J = 7.6 Hz, 6 H).

[0250] 2. Ethyl (2,6-diethylphenyl)(2-methoxyethyl)carbamate (D89)

[0251] To a suspension of NaH (prepared from 0.77 g of 60% suspension in mineral oil, 19.3 mmol, washed with hexane) in THF (100 ml) a solution of ethyl (2,6- diethylphenyl)carbamate (3.55 g, 16.1 mmol) in THF (20 ml) was added dropwise at 0°C, followed by a solution of l-bromo-2-methoxyethane (2.30 ml, 3.35 g, 24.1 mmol) in THF (10 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: dichloromethane / ethyl acetate = 10 / 1, v / v) to give 1.50 g (33%) of the product (mixture of two isomers in ratio 4 to 1) as a yellowish oil.

[0252] 1H NMR (400 MHz, CDCl3):, a major isomer: 3 7.28 - 7.19 (m, 1 H), 7.17 - 7.10 (m, 2 H), 4.09 (q, J = 7.1 Hz, 2 H), 3.72 - 3.68 (m, 2 H), 3.54 - 3.46 (m, 2 H), 3.30 (s, 3 H), 2.60 - 2.52 (m, 4 H), 1.21 (t, J= 7.1 Hz, 6 H), 1.12 (t, J= 7.1 Hz, 3 H).

[0253] 1H NMR (400 MHz, CDCl3), a minor isomer: 3 7.28 - 7.19 (m, 1 H), 7.17 - 7.10 (m, 2 H), 4.24 (q, J = 1A Hz, 2 H), 3.69 - 3.63 (m, 2 H), 3.54 - 3.46 (m, 2 H), 3.30 (s, 3 H), 2.69 - 2.60 (m, 4 H), 1.34 (t, J = 7.1 Hz, 6 H), 1.23 (t, J = 7.6 Hz, 3 H).

[0254] 13C NMR (101 MHz, CDCl3), both isomers: 3 156.4, 141.8, 141.7, 138.2, 127.8, 127.7, 126.3, 126.3, 126.2, 70.2, 69.9, 61.5, 61.4, 58.5, 58.5, 50.0, 49.8, 24.7, 23.7, 23.6, 14.7, 14.4, 14.3. Example 12. Synthesis of ethyl (2-methoxyethyl)(o-tolyl)carbamate (D90)

[0255] 1. Ethyl o-tolylcarbamate

[0256] To a mixture of o-toluidine (7.00 g, 65.4 mmol) and K2CO3(16.4 g, 119 mmol) in chloroform (100 ml) a solution of ethyl chloroformate (5.61 ml, 6.45 g, 59.5 mmol) in chloroform (10 ml) was added dropwise at room temperature. The mixture was stirred for 12 h at 60°C and then poured into water (150 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvents were removed under reduced pressure. The residue was distilled on a Kugelrohr apparatus at 90°C / 0.80 mbar to give 9.18 g (79%) of the product as a red oil.

[0257] 1H NMR (400 MHz, CDCl3): δ 7.80 (br. s., 1 H), 7.26 - 7.19 (m, 1 H), 7.17 (d, J = 7.5 Hz, 1 H), 7.06 - 7.00 (m, 1 H), 6.43 (br. s., 1 H), 4.25 (q, J = 7.2 Hz, 2 H), 2.27 (s, 3 H), 1.33 (t, J = 7.1 Hz, 3 H).

[0258] 13C NMR (101 MHz, CDCl3): δ 153.9, 135.9, 130.3, 126.8, 124.0, 121.1, 61.2, 17.6, 14.5.

[0259] 2. Ethyl (2-methoxyethyl)(o-tolyl)carbamate (D90)

[0260] To a suspension of NaH (prepared from 0.98 g of 60% suspension in mineral oil, 24.6 mmol, washed with hexane) in THF (100 ml) a solution of ethyl o-tolylcarbamate (4.00 g, 22.3 mmol) in THF (10 ml) was added dropwise at 0°C, followed by a solution of 1- bromo-2-methoxyethane (2.40 ml, 3.42 g, 24.6 mmol) in THF (10 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethanc (3 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled on a Kugelrohr apparatus at 120°C / 0.80 mbar to give 3.95 g (75%) of the product as a red oil.

[0261] 1H NMR (400 MHz, CDCl3): δ 7.26 - 7.11 (m, 4 H), 4.30 - 3.80 (m, 3 H), 3.67 - 3.60 (m, 1 H), 3.55 - 3.46 (m, 2 H), 3.32 (s, 3 H), 2.26 - 2.19 (m, 3 H), 1.40 - 1.09 (m, 3 H).

[0262] 13C NMR (101 MHz, CDCl3): δ 155.8, 140.4, 136.1, 130.7, 128.3, 127.4, 126.5, 69.7, 61.5, 58.5, 49.2, 17.4, 14.6.

[0263] Example 13. Synthesis of ethyl ethyl(l-methoxybutan-2-yl)carbamate (D91)

[0264] 1. Ethyl (l-methoxybutan-2-yl)carbamate

[0265] To a solution of 1-methoxybutan-2-amine (3.46 g, 33.5 mmol) and triethylamine (7.01 ml, 5.09 g, 50.3 mmol) in dichloromethane (40 ml) a solution of ethyl chloroformate (3.52 ml, 4.00 g, 36.9 mmol) in dichloromethane (20 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (300 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 2.91 g (50%) of the product as a clear colorless liquid, b.p. 75-85°C / l mbar.

[0266] 1H NMR (400 MHz, CDCl3): δ 4.90 (br. s., 1 H), 4.05 (q, J = 7.0 Hz, 2 H), 3.60 (br. s., 1 H), 3.38 - 3.29 (m, 2 H), 3.28 (s, 3 H), 1.62 - 1.48 (m, 1 H), 1.48 - 1.36 (m, 1 H), 1.18 (t, J = 7 A Hz, 3 H), 0.87 (t, J= 7.5 Hz, 3 H).

[0267] 13C NMR (101 MHz, CDCl3): δ 56.3, 73.9, 60.4, 58.8, 52.0, 24.8, 14.4, 10.3.

[0268] 2. Ethyl ethyl(l-methoxybutan-2-yl)carbamate (D91) To a suspension of NaH (prepared from 0.73 g of 60% suspension in mineral oil, 18.3 mmol, by washing with hexane) in a mixture of THF (70 ml) and DMF (35 ml), a solution of ethyl (l-methoxybutan-2-yl)carbamate (2.91 g, 16.7 mmol) in THF (10 ml) was added dropwise at 0°C, followed by a solution of ethyl iodide (1.94 ml, 3.89 g, 24.9 mmol) in THF (10 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (50 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (3 x 50 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 2.94 g (87%) of the product as a clear colorless liquid, b.p. 61-64°C / 1 mbar.

[0269] 1H NMR (400 MHz, CDCl3): δ 4.18 - 4.06 (m, 2 H), 4.06 - 3.81 (m, 1 H), 3.43 (br. s., 1 H), 3.36 - 3.31 (m, 1 H), 3.29 (s, 3 H), 3.20 (br. s., 1 H), 3.12 (br. s., 1 H), 1.60 - 1.38 (m, 2 H ), 1 .23 (t, J = 7.1 Hz, 3 H), 1 .10 (t, J = 7.0 Hz, 3 H), 0.87 (t, J = 7.4 Hz, 3 H).

[0270] 13C NMR (101 MHz, CDCl3): δ 156.7, 74.0, 73.7, 60.7, 58.6, 57.5, 38.8, 38.5, 22.8, 22.3, 15.0, 14.6, 10.8.

[0271] Example 14. Synthesis of isobutyl ethyl(2-methoxyethyl)carbamate (D95)

[0272] 1. Isobutyl (2-methoxyethyl)carbamate

[0273] To a suspension of NaH (prepared from 2.80 g of 60% suspension in mineral oil, 69.9 mmol, washed with hexane) in THF (50 ml) a solution of 2-methoxyethan-1-amine (5.73 ml, 5.00 g, 66.6 mmol) in THF (10 ml) was added dropwise at 0°C, followed by a solution of isobutyl chloroformate (8.63 ml, 9.09 g, 66.6 mmol) in THF (20 ml) added dropwise at the same temperature. The resulting mixture was, allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (400 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic extracts were washed with water (3 x 100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 7.34 g (63%) of the product as a clear colorless liquid, b.p. 63-67°C / l mbar.

[0274] 1H NMR (400 MHz, CDCl3): δ 5.17 (br. s., 1 H), 3.77 (d, J= 6.7 Hz, 2 H), 3.42 - 3.35 (m, 2 H), 3.33 - 3.22 (m, 2 H), 3.28 (s, 3 H), 1.91 - 1.75 (m, 1 H), 0.85 (d, J= 6.7 Hz, 6 H).

[0275] 13C NMR (101 MHz, CDCl3): δ 156.7, 71.3, 70.8, 58.5, 40.6, 27.8, 18.8.

[0276] 2. Isobutyl ethyl(2-methoxyethyl)carbamate (D95)

[0277] To a suspension of NaH (prepared from 1.26 g 60% suspension in mineral oil, 31.4 mmol, washed with hexane) in a mixture of THF (100 ml) and DMF (50 ml) a solution of isobutyl (2-methoxyethyl)carbamate (5.00 g, 28.5 mmol) in THF (15 ml) was added dropwise at 0°C, followed by a solution of ethyl iodide (3.44 ml, 6.68 g, 42.8 mmol) in THF (15 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (50 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (3 x 50 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 4.66 g (80%) of the product as a clear colorless liquid, b.p. 92-94°C / 3 mbar.

[0278] 1H NMR (400 MHz, CDCl3): δ 3.79 (d, J = 6.5 Hz, 2 H), 3.47 - 3.39 (m, 2 H), 3.38 - 3.32 (m, 2 H), 3.31 - 3.32 (m, 2 H), 3.28 (s, 3 H), 1.94 - 1.80 (m, 1 H), 1.05 (t, J= 7.1 Hz, 3 H), 0.88 (d, J = 6.7 Hz, 6 H).

[0279] 13C NMR (101 MHz, CDCl3): δ 156.1, 71.2, 58.6, 46.6.42.8, 27.9, 19.0, 13.3.

[0280] Example 15. Synthesis of ethyl (S)-2-(methoxymethyl)pyrrolidine-l-carboxylate (D100) 1. Ethyl (S)-2-(hydroxymethyl)pyrrolidine-1-carboxylate

[0281] To a solution of (5)-pyrrolidin-2-ylmethanol (4.00 g, 39.5 mmol) and triethylamine (5.51 ml, 4.00 g, 39.5 mmol) in dichloromethane (120 ml) a solution of ethyl chloroformate (3.78 ml, 4.29 g, 39.5 mmol) in dichloromethane (30 ml) was added dropwise at -20°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (300 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 4.40 g (64%) of the product as a clear colorless oil, which then used without additional purification.

[0282] 1H NMR (400 MHz, CDCl3): δ 4.55 (br. s., 1 H), 4.08 (q, J = 7.1 Hz, 2 H), 4.00 - 3.73 (m, 1 H), 3.67 - 3.49 (m, 2 H), 3.48 - 3.37 (m, 1 H), 3.37 - 3.22 (m, 1 H), 1.99 - 1.50 (m, 4 H), 1.21 (t, J= 7.1 Hz, 3 H).

[0283] 13C NMR (101 MHz, CDCl3): δ 157.2, 66.7, 61.3, 60.3, 47.0, 28.4, 23.9, 14.5.

[0284] 2. Ethyl (S)-2-(methoxymethyl)pyrrolidine-1-carboxylate (DI 00)

[0285] To a suspension of NaH (prepared from 1.12 g of 60% suspension in mineral oil, 27.9 mmol, washed with hexane) in THF (60 ml) a solution of ethyl (S)-2- (hydroxymethyl)pyrrolidine-l -carboxylate (4.40 g, 25.4 mmol) in THF (20 ml) was added dropwise at 0°C, followed by a solution of methyl iodide (2.37 ml, 5.41 g, 38.1 mmol) in THF (10 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (50 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic extracts dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 5 / 1, v / v) to give 1.88 g (40%) of the product as a clear colorless liquid.

[0286] 1H NMR (400 MHz, CDCl3): δ 4.18 - 4.00 (m, 2 H), 3.92 (br. s., 1 H), 3.52 - 3.40 (m, 1 H), 3.40 - 3.13 (m, 3 H), 3.30 (s, 3 H), 1.95 - 1.71 (m, 4 H), 1.21 (t, J= 7.1 Hz, 3 H).

[0287] 13C NMR (101 MHz, CDCl3): δ 155.1 , 73.0 (br. s.), 60.7, 58.9, 56.4 (br. s.), 46.5, 28.0 (br. s.), 23.5 (br. s.), 14.6.

[0288] Example 16. Synthesis of ethyl isopropyl(2-methoxypropyl)carbamate (D101)

[0289] 1. 1-(Isopropylamino)propan-2-ol

[0290] A mixture of propylene oxide (23.3 ml, 20.0 g, 344 mmol), isopropylamine (59.0 ml, 40.7 g, 689 mmol) and LiBr (10.0 g, 115 mmol) in THF (500 ml) was stirred for 2 days at 50°C. Then the volatiles were removed under reduced pressure at 40°C / 200 mbar. The residue was diluted with water (200 ml) and extracted with dichloromethane (6 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure at 40°C / 200 mbar. The residue was distilled under reduced pressure to give 21.5 g (80%) of the product as a clear colorless oil, b.p. 86°C / 50 mbar.

[0291] 1H NMR (400 MHz, CDCl3): δ 3.91 (br. s., 1 H), 3.76 - 3.63 (m, 1 H), 2.79 - 2.69 (m, 1 H), 2.69 - 2.57 (m, 1 H), 2.38 - 2.23 (m, 1 H), 1.13 - 1.05 (m, 3 H), 1.05 - 0.92 (m, 6 H).

[0292] 13C NMR (101 MHz, CDCl3): δ 65.7, 54.4, 48.6, 23.0, 22.9, 20.8.

[0293] 2. N-isopropyl -2 -methoxypropan- 1 -amine

[0294] To a suspension of KH (prepared from 14.8 g of 30% suspension in mineral oil, 111 mmol, washed with hexane) in diethyl ether (100 ml), a solution of 1-(isopropylamino)propan-2- ol (13,0 g, 111 mmol) in diethyl ether (200 ml) was added dropwise at 0°C, followed by a solution of methyl iodide (6.68 ml, 15.2 g, 107 mmol) in diethyl ether (100 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (20 ml). Then the residue was diluted with water (200 ml), the organic layer was separated and the aqueous layer was extracted with diethyl ether (3 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure 40°C / 750 mbar. The residue was distilled under reduced pressure to give 10.1 g (69%) of the product as a clear colorless liquid, b.p. 60-65°C / 50 mbar.

[0295] 1H NMR (400 MHz, CDCl3): δ 3.41 - 3.31 (m, 1 H), 3.26 (s, 3 H), 2.71 - 2.62 (m, 1 H), 2.56 - 2.42 (m, 2 H), 1.51 (br. s., 1 H), 1.05 (d, J= 6.2 Hz, 3 H), 0.96 (t, J= 6.1 Hz, 6 H).

[0296] 13C NMR (101 MHz, CDCl3): δ 76.2, 56.0, 53.2, 48.5, 22.9, 22.5, 16.92, 16.89.

[0297] 3. Ethyl isopropyl(2-methoxypropyl)carbamate (D101)

[0298] To a solution of N-isopropyl-2-methoxypropan-1-amine (10.1 g, 76.7 mmol) and triethylamine (10.7 ml, 7.76 g, 76.7 mmol) in dichloromethane (250 ml) a solution of ethyl chloroformate (7.33 ml, 8.32 g, 76.7 mmol) in dichloromethane (50 ml) was added dropwise at -20°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (300 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water ( 100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 5 / 1, v / v) to give 12.2 g (78%) of the product as a clear colorless liquid.

[0299] 1H NMR (400 MHz, CDCl3): δ 4.13 - 4.03 (m, 2 H), 3.98 (br. s., 3 H), 3.48 (br. s., 1 H), 3.28 (s, 3 H), 3.14 (br. s., 1 H), 3.06 - 2.99 (m, 1 H), 1.21 (t, J = 7.1 Hz, 3 H), 1.14 (d, J = 5.4 Hz, 3 H), 1.12 (d, J= 5.4 Hz, 3 H), 1.06 (d, J = 6.2 Hz, 3 H).

[0300] 13C NMR (101 MHz, CDCl3): δ 156.1 (br. s.), 76.3 (br. s.), 60.7, 56.6, 50.2 (br. s.), 49.1, 20.6 (br. s.), 16.9, 14.5.

[0301] Example 17. Synthesis of (S)-2-(methoxymethyl)indoline-1-carboxylate (DI 02)

[0302] 1. (S)-2-(methoxymethyl)indoline

[0303] To a suspension of KH (prepared from 7.87 g 30% suspension in mineral oil, 58.9 mmol, washed with hexane) in diethyl ether (60 ml) a solution of (S)-indolin-2-ylmethanol (8.78 g, 58.9 mmol) in diethyl ether (120 ml) was added dropwise at 0°C, followed by a solution of methyl iodide (3.55 ml, 8.10 g, 57.1 mmol) in diethyl ether (60 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (20 ml). Then the residue was diluted with water (200 ml), the organic layer was separated and the aqueous layer was extracted with diethyl ether (3 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 5 / 1, v / v) to give 4.69 g (49%) of the product as a clear colorless oil.

[0304] 1H NMR (400 MHz, CDCl3): δ 7.14 - 7.10 (m, 1 H), 7.09 - 7.03 (m, 1 H), 6.74 (dt, J= 0.9, 7.4 Hz, 1 H), 6.66 (d, J= 7.8 Hz, 1 H), 4.34 (s, 1 H), 4.11 (dddd, J= 5.2, 6.7, 7.9, 9.2 Hz, 1 H), 3.48 - 3.39 (m, 5 H), 3.17 (dd, J= 9.2, 15.7 Hz, 1 H), 2.72 (dd, J= 6.7, 15.7 Hz, 1 H).

[0305] 13C NMR (101 MHz, CDCl3): δ 150.4, 127.8, 127.3, 124.6, 118.4, 109.4, 76.2, 58.8, 58.1, 32.3.

[0306] 2. Ethyl (S)-2-(methoxymethyl)indoline-1-carboxylate (D102)

[0307] To a solution of (S)-2-(methoxymethyl)indoline (4.69 g, 28.7 mmol) and triethylamine (4.00 ml, 2.91 g, 28.7 mmol) in dichloromethane (100 ml) a solution of ethyl chloroformate (2.75 ml, 3.12 g, 28.7 mmol) in dichloromethane (25 ml) was added dropwise at -20°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (300 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 5 / 1, v / v) to give 4.19 g (62%) of the product as a clear colorless oil.

[0308] 1H NMR (400 MHz, CDCl3): δ 7.72 (br. s., 1 H), 7.21 - 7.12 (m, 2 H), 6.99 - 6.90 (m, 1 H), 4.63 (br. s., 1 H), 4.31 (q, J = 7.1 Hz, 2 H), 3.62 (dd, J= 3.9, 9.1 Hz, 1 H), 3.43 - 3.32 (m, 4 11), 3.27 (dd, J = 9.7, 16.3 Hz, 1 H), 3.04 (dd, J= 2.3, 16.3 Hz, 1 H), 1.38 (t, J= 1A Hz, 3 H).

[0309] 13C NMR (101 MHz, CDCl3): δ 153.1 (br. s.), 141.9 (br. s.), 130.0 (br. s.), 127.1, 124.8, 122.7, 115.2, 72.8 (br. s.), 61.5 (br. s.), 58.9, 57.9, 31.2 (br. s.), 14.49, 14.46.

[0310] Example 18. Synthesis of ethyl ethyl((tetrahydrofuran-2-yl)methyl)carbamate (D109)

[0311] 1. Ethyl ethylcarbamate

[0312] To a mixture of dichloromethane (350 ml) and a solution of NaHCO3(27.8 g, 331 mmol) in water (250 ml) a solution of ethylammonium chloride (10.0 g, 123 mmol) in water (20 ml) was added dropwise at room temperature, followed by a solution of ethyl chloroformate (12.3 ml, 14.0 g, 129 mmol) in dichloromcthane (50 ml) added dropwise at the same temperature. Then the obtained mixture was stirred for 12 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 14.1 g (98%) of the product as a clear colorless oil, which then used without additional purification.

[0313] 1H NMR (400 MHz, CDCl3): δ 4.89 (br. s., 1 H), 4.04 (q, J = 7.1 Hz, 2 H), 3.14 (q, J = 7.2 Hz, 2 H), 1.17 (t, J= 7.1 Hz, 3 H), 1.06 (t, J= 7.2 Hz, 3 H).

[0314] 13C NMR (101 MHz, CDCl3): δ 157.0, 60.6. 35.9, 15.3, 14.7.

[0315] 2. Ethyl ethyl((tetrahydrofuran-2-yl)methyl)carbamate (D109) To a suspension of NaH (prepared from 5.28 g of 60% suspension in mineral oil, 132 mmol, washed with hexane) in DMF (120 ml) a solution of ethyl ethylcarbamate (14.1 g, 120 mmol) in DMF (20 ml) was added dropwise at 0°C, followed by a solution of 2- (chloromethyl)tetrahydrofuran (17.0 ml, 18.8 g, 156 mmol) in DMF (20 ml) added dropwise at room temperature. The mixture was stirred for 12 h at 80°C and then quenched with methanol (5 ml). Further, DMF was removed on a Kugelrohr apparatus at 40°C / 0.20 mbar. The residue was diluted with dichloromethane (100 ml) and filtered through a thin pad of Celite 503, which was then washed with an additional amount of dichloromethane (2 x 50 ml). The filtrate was dried over Na-SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 5 / 1 , v / v) to give 1.99 g (8%) of the product as a clear colorless liquid.

[0316] 1H NMR (400 MHz, CDCl3): δ 4.06 (q, J= 7.1 Hz, 2 H), 4.01 (br. s., 1 H), 3.84 - 3.74 (m, 1 H), 3.73 - 3.62 (m, 1 H), 3.51 - 3.12 (m, 4 H), 1.98 - 1.70 (m, 3 H), 1.58 - 1.42 (m, 1 H), 1.19 (t, J = 7.1 Hz, 3 H), 1.08 - 0.98 (m, 3 H).

[0317] 13C NMR (101 MHz, CDCl3): δ 156.5, 155.9, 78.0, 67.7, 60.8, 50.5, 49.9, 42.8, 42.5, 28.9, 25.3, 14.5, 13.3, 12.8.

[0318] Example 19. Synthesis of ethyl morpholine-4-carboxylate (D112)

[0319] To a two-phase mixture of a solution ofNaHCO3(8.20 g, 97.7 mmol) in water (60 ml) and a solution of morpholine (5.00 g, 57.4 mmol) in dichloromethane (200 ml) a solution of ethyl chloroformate (5.77 ml, 6.55 g, 60.3 mmol) in dichloromethane (50 ml) was added dropwise at room temperature. Then the obtained mixture stirred for 12 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 20 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 8.46 g (93%) of the product as a clear colorless oil, which then used without additional purification.

[0320] 1H NMR (400 MHz, CDCl3): δ 4.13 (q. J = 7.1 Hz, 2 H), 3.72 - 3.54 (m, 4 H), 3.48 - 3.39 (m, 4 H), 1.25 (t, J = 7.1 Hz, 3 H).13C NMR (101 MHz, CDCl3): δ 155.5, 66.5, 61.4, 44.0 (br. s.), 14.6.

[0321] Example 20. Synthesis of ethyl 8-methoxy-3,4-dihydroquinoline-1(2H)-carboxylate (D113)

[0322] To a solution of 8-methoxy-1,2,3,4-tetrahydroquinoline (5.37 g, 32.9 mmol) and pyridine (5.10 ml, 4.98 g, 49.4 mmol) in dichloromethane (100 ml) a solution of ethyl chloroformate (3.50 ml, 3.93 g, 36.2 mmol) in dichloromethane (20 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into a saturated solution of NaHCO3in water (200 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. Further, pyridine was removed on a Kugelrohr apparatus at 40°C / 0.20 mbar. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 4 / 1, v / v) to give 7.60 g (99%) of the product as a white solid.

[0323] 1H NMR (400 MHz, CDCl3): δ 7.1 1 - 7.05 (m, 1 H), 6.80 - 6.73 (m, 2 H), 4.19 (br. s., 3 H), 3.83 (s, 3 H), 3.55 (br. s., 1 H), 2.72 (t, J= 6.8 Hz, 2 H), 1.96 (br. s., 2 H), 1.24 (t, J = 7.1 Hz, 3 H).

[0324] ,3C NMR (101 MHz, CDCl3): δ 155.3, 153.3, 134.4, 127.9, 125.5, 119.8, 109.0, 61.4, 55.3, 44.0, 26.2, 24.2, 14.4.

[0325] Example 21. Synthesis of ethyl (2-isobutyl-2-(methoxymethyl)-4- methylpentyl)(methyl)carbamate (D114)

[0326] 1 . Ethyl 2-cyano-2-isobutyl-4-methylpentanoate A mixture of ethyl 2-cyanoacetate (22.5 g, 200 mmol), isobutyl iodide (50.6 ml, 81.0 g, 440 mmol) and K2CO3(55.0 g, 400 mmol) in DMF (300 ml) was stirred for 2 days at room temperature and then poured into water (1000 ml). The crude product was extracted with dichloromethane (3 x 150 ml). The combined organic extracts were washed with water (200 ml), dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 30.1 g (67%) of the product as a clear colorless liquid, b.p. 68°C / 1 mbar.

[0327] 1H NMR (400 MHz, CDCl3): δ 4.23 (q, J= 7.1 Hz, 2 H), 1.89 - 1.76 (m, 4 H), 1.70 - 1.59 (m, 2 H), 1.31 (t, J = 7.2 Hz, 4 H), 1.01 (d, J = 6.4 Hz, 6 H), 0.86 (d, J= 6.3 Hz, 6 H).

[0328] 13C NMR (101 MHz, CDCl3): δ 169.8, 119.6, 62.4, 47.6, 47.3, 25.9, 23.2, 22.4, 13.8.

[0329] 2. 2-(Aminomethyl)-2-isobutyl-4-methylpentan-1-ol

[0330] To a suspension of LiAlH4(16.0 g, 422 mmol) in THF (400 ml) a solution of ethyl 2- cyano-2-isobutyl-4-methylpentanoate (15.0 g, 66.7 mmol) in THF (100 ml) was added dropwise at 0°C and then stirred for 2 days at 60°C. The mixture was carefully quenched successively with water (16.3 ml), a solution of NaOH in water (15%, 16 ml), then again with water (48 ml) at 0°C. Further, the mixture was filtered through a thin pad of Celite 503, which was then washed with additional amount of dichloromethane (2 x 100 ml). The filtrate was evaporated under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled in vacuo to give 10.4 g (83%) of the product as a clear colorless liquid, b.p. 70-80°C / l mbar, which crystallized while standing.

[0331] 1H NMR (400 MHz, CDCl3): δ 3.60 (s, 2 H), 2.82 (s, 2 H), 2.70 (br. s., 3 H), 1.77 - 1.61 (m, 2 H), 1.31 - 1.21 (m, 4 H), 0.94 (d, J = 4.2 Hz, 6 H), 0.92 (d, J = 4.1 Hz, 6 H).13C NMR (101 MHz, CDCl3): δ 72.0, 50.9, 41.5, 41.2, 25.4, 25.3, 23.2.

[0332] 3. 2-((Dimethylamino)methyl)-2-isobutyl-4-methylpentan-1-ol

[0333] To a solution of 2-(aminomethyl)-2-isobutyl-4-methylpentan-1-ol (3.0 g, 16.0 mmol), formalin (37% in mixture of water and methanol, 11.8 ml, 160 mmol) and acetic acid (10 ml) in methanol (180 ml), NaBH,CN (10.1 ml, 160 mmol) was added portionwise. The obtained mixture was stirred for 12 h at room temperature and then the volatiles were removed under reduced pressure. The residue was diluted with a saturated solution of K2CO3in water (100 ml) and extracted with diethyl ether (3 x 100 ml). The combined organic extracts were dried over K2CO3and the solvent was removed under reduced pressure. The residue was mixed with milled KOH (3 g) and then distilled on a Kugelrohr apparatus at 120°C / 0.1 mbar to give 3.09 g (77%) of the product as a colorless oil.

[0334] 1H NMR (400 MHz, CDCl3): δ 3.60 (s, 2 H), 2.48 (s, 2 H), 2.33 (s, 6 H), 1.74 - 1.62 (m, 2 H), 1.46 (dd, J = 5.8, 14.3 Hz, 2 H), 1.09 (dd, J= 5.1, 14.3 Hz, 2 H), 0.96 (d, J= 6.6 Hz, 6 H), 0.92 (d, J = 6.7 Hz, 6 H).

[0335] 13C NMR (101 MHz, CDCl3): δ 71.0, 70.6, 48.8, 42.5, 42.0, 25.7, 25.2, 23.4.

[0336] 4. 2-Isobutyl-2-(methoxymethyl)-N,N,4-trimethylpentan-1-amine

[0337] To a suspension of KH (prepared from 1.01 g of 30% suspension in mineral oil, 25.3 mmol, washed with hexane) in THF (40 ml), a solution of 2-((dimethylamino)methyl)-2- isobutyl-4-methylpentan-1-ol (4.18 g, 19.4 mmol) in THF (20 ml) was added dropwise at 0°C, followed by a solution of methyl iodide (1.30 ml, 2.90 g, 20.4 mmol) in THF (10 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml), the volatiles were removed under reduced pressure and the residue was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure. The residue was distilled on a Kugelrohr apparatus at 85°C / 0.1 mbar to give 4.07 g (91%) of the product as a colorless oil.1H NMR (400 MHz, CDCl3): δ 3.27 (s, 3 H), 3.18 (s, 2 H), 2.27 (s, 6 H), 2.22 (s, 2 H), 1.76 - 1.62 (m, 2 H), 1.26 (s, 2 H), 1.25 (s, 2 H), 0.92 (d, J= 2.5 Hz, 6 H), 0.91 (d, . / = 2.5 Hz, 6 H).

[0338] 13C NMR (101 MHz, CDCl3): δ 76.8, 64.9, 58.3, 48.8, 43.1, 42.3, 25.6, 25.4, 23.3.

[0339] 5. Ethyl (2-isobutyl-2-(methoxymethyl)-4-methylpentyl)(methyl)carbamate (D114)

[0340] A solution of 2-isobutyl-2-(methoxymethyl)-N,N,4-trimethylpentan-1-amine (4.07 g, 17.8 mmol) and ethyl chloroformate (2.00 ml, 2.31 g, 21.3 mmol) in dichloroethane (80 ml) was stirred for 2 days at 80°C. Then the obtained mixture was quenched with a saturated solution of NaHCO, in water (100 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extracts were evaporated under reduced pressure. The residue was distilled on a Kugelrohr apparatus at 82-84°C / 0.1 mbar to give 2.97 g (58%) of the product as a colorless oil.

[0341] 1H NMR (400 MHz, CDCl3): δ 4.13 (q, J = 7.1 Hz, 2 H), 3.34 - 3.29 (m, 2 H), 3.28 (s, 3 H), 3.17 (br. s., 2 H), 2.92 (d, J= 9.7 Hz, 3 H), 1.73 (br. s., 2 H), 1.37 - 1.30 (m, 2 H), 1.29 - 1 .21 (m, 2 H), 1.27 (t, J = 7.1 Hz, 3 H), 0.95 - 0.88 (m, 12 H).

[0342] 13C NMR (101 MHz, CDCl3): δ 157.6 (br. s.), 77.2, 61.0, 58.2, 54.7, 53.9, 43.9 (br. s.), 42.8, 37.1 , 36.5, 25.5, 25.3, 23.2, 14.6.

[0343] Example 22, Synthesis of ethyl 2-(2-methoxyethyl)piperidine-1-carboxylate (D115)

[0344] To a suspension of KH (prepared from 3.10 g 30% suspension in mineral oil, 77.5 mmol, washed with hexane) in diethyl ether (200 ml) a solution of 2-(piperidin-2-yl)ethan-l-ol (10.0 g, 77.5 mmol) in diethyl ether (100 ml) was added dropwise at 0°C, followed by a solution of methyl iodide (4.80 ml, 10.9 g, 77.5 mmol) in diethyl ether (100 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (20 ml). Then the residue was diluted with water (200 ml), the organic layer was separated and the aqueous layer was extracted with diethyl ether (3 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure to give 6.16 g of the oily mixture that contained approximately 66% of the target product. This mixture was then used without additional purification.

[0345] To a solution of the above mixture (6.16 g) and pyridine (5.20 ml, 5.11 g, 64.6 mmol) in dichloromethane (120 ml) a solution of ethyl chloroformate (4.50 ml, 5.13 g, 47.4 mmol) in dichloromethane (20 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into a saturated solution of NaHCO, in water (200 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. Further, pyridine was removed on a Kugelrohr apparatus at 40°C / 0.20 mbar. The residue was distilled in vacuo to give 3.10 g (19%) of the product as a clear colorless liquid, b.p. 72-74°C / l mbar.

[0346] 1H NMR (400 MHz, CDCl3): δ 4.50 - 4.33 (m, 1 H), 4.19 - 4.08 (m, 2 H), 4.04 (br. s., 1 H), 3.36 (t, J= 6.8 Hz, 2 H), 3.33 (s, 3 H), 2.89 - 2.78 (m, 1 H), 2.08 - 1.98 (m, 1 H), 1.76 - 1.49 (m, 6 H), 1.49 - 1.34 (m, 1 H), 1.27 (t, J = 7.1 Hz, 3 H).

[0347] 13C NMR (101 MHz, CDCl3): δ 155.6, 69.9, 60.9, 58.4, 47.8, 38.7, 29.6, 28.7, 25.4, 18.8, 14.5.

[0348] Example 23. Synthesis of ethyl 3-(methoxymethyl)piperidine-l-carboxylate (D119)

[0349] 1. Ethyl 3-(hydroxymethyl)piperidine-l -carboxylate

[0350] To a mixture of dichloromethane (80 ml) and a solution of NaHCO3(3.72 g, 44.3 mmol) in water (30 ml) a solution of piperidin-3-ylmethanol (3.00 g, 26.0 mmol) in dichloromethane (20 ml) was added dropwise at room temperature, followed by a solution of ethyl chloroformate (2.62 ml, 2.97 g, 27.4 mmol) in dichloromethane (10 ml) added dropwise at the same temperature. Then the obtained mixture was stirred for 12 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 4.08 g (84%) of the product as a yellowish oil, which then used without additional purification.

[0351] 1H NMR (400 MHz, CDCl3): δ 4.23 - 3.98 (m, 2 H), 3.98 - 3.54 (m, 2 H), 3.50 - 3.28 (m, 2 H), 3.28 - 2.34 (m, 3 H), 1.79 - 1.47 (m, 3 H), 1.45 - 1.27 (m, 1 H), 1.27 - 0.98 (m, 4 H).

[0352] 13C NMR (101 MHz, CDCl3): δ 155.7, 64.3 (br. s.), 61.1, 46.5 (br. s.), 44.4 (br. s.), 38.1 (br. s.), 26.8, 24.1, 14.5.

[0353] 2. Ethyl 3-(methoxymethyl)piperidine-1 -carboxylate (D119)

[0354] To a suspension of NaH (prepared from 0.96 g of 60% wt. suspension in mineral oil, 24.0 mmol, washed with hexane) in THF (250 ml) methyl iodide (6.00 ml, 15.5 g, 109 mmol) was added dropwise at 0°C, followed by a solution of ethyl 3-(hydroxymethyl)piperidine- 1 -carboxylate (4.08 g, 21.8 mmol) in THF (20 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml), and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 3.93 g (90%) of the product as a yellowish oil, which then used without additional purification.

[0355] 1H NMR (400 MHz, CDCl3): δ 4.16 - 4.05 (m, 2 H), 4.05 - 3.97 (m, 1 H), 3.97 - 3.86 (m, 1 H), 3.30 (s, 3 H), 3.26 - 3.15 (m, 2 H), 2.85 - 2.75 (m, 1 H), 2.62 (dd, J= 10.0, 13.0 Hz, 1 H), 1.83 - 1.69 (m, 2 H), 1.69 - 1.58 (m, 1 H), 1.52 - 1.35 (m, 1 H), 1.23 (t, 7.1 Hz, 3 H). 1.23 - 1.10 (m, 1 H).

[0356] 13C NMR (101 MHz, CDCl3): δ 155.6, 75.1, 61.0, 58.8, 47.1, 44.4, 36.1, 27.4, 24.4, 14.6. Example 24. Synthesis of ethyl 3-methoxypiperidine-l-carboxylate (D120)

[0357] 1. Ethyl 3-hydroxypiperidine-1-carboxylate

[0358] To a mixture of dichloromethane (150 ml) and a solution of NaHCO3(7.06 g, 84.0 mmol) in water (60 ml) a solution of piperidin-3-ol (5.00 g, 49.4 mmol) in dichloromethane (20 ml) was added dropwise at room temperature, followed by a solution of ethyl chloroformate (4.37 ml, 5.90 g, 54.4 mmol) in dichloromethane (10 ml) added dropwise at the same temperature. Then the obtained mixture was stirred for 12 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 8.18 g (96%) of the product as a colorless oil, which then used without additional purification.

[0359] 1H NMR (400 MHz, CDCl3): δ 4.06 (q, J = 7.1 Hz, 2 H), 3.80 (dd, J = 3.8, 12.9 Hz, 1 H), 3.72 - 3.47 (m, 2 H), 3.34 (s, 1 H), 3.13 - 2.99 (m, 1 H), 2.95 (dd, J = 8.1, 12.9 Hz, 1 H), 1.94 - 1.79 (m, 1 H), 1.77 - 1.64 (m, 1 H), 1.52 - 1.32 (m, 2 H), 1.20 (t, J = 7.1 Hz, 3 H).

[0360] 13C NMR (101 MHz, CDCl3): δ 155.8, 65.7, 61.3, 50.5, 43.8, 32.3, 22.4, 14.5.

[0361] 2. Ethyl 3-methoxypiperidine-1-carboxylate (D120)

[0362] To a suspension of NaH (prepared from 2.08 g of 60% wt. suspension in mineral oil, 51.9 mmol, washed with hexane) in THF (500 ml) methyl iodide (14.7 ml, 33.5 g, 236 mmol) was added dropwise at 0°C, followed by a solution of ethyl 3 -hydroxypiperidine-1- carboxylate (8.18 g, 47.2 mmol) in THF (20 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water ( 100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 7.64 g (86%) of the product as a colorless oil, which then used without additional purification.

[0363] 1H NMR (400 MHz, CDCl3): δ 4.14 - 4.00 (m, 2 H), 3.74 (br. s., 1 H), 3.58 - 3.47 (m, 1 H), 3.32 (s, 3 H), 3.23 - 2.99 (m, 3 H), 1.93 - 1.80 (m, 1 H), 1.75 - 1.64 (m, 1 H), 1.53 - 1.31 (m, 2 H), 1 .20 (t, J= 1A Hz, 3 H).

[0364] 13C NMR (101 MHz, CDCl3): δ 155.5, 74.5, 61.1, 56.0, 47.0, 43.9, 29.8, 22.3 (br. s.), 14.5.

[0365] Example 25. Synthesis of ethyl 2-(methoxymethyl)piperidine-l-carboxylate (D121)

[0366] To a solution of 2-(methoxymethyl)piperidine (1.03 g, 7.98 mmol) and pyridine (5.20 ml, 5.1 1 g, 64.6 mmol) in dichloromethane (20 ml) a solution of ethyl chloroformate (0.96 ml, 0.95 g, 12.0 mmol) in dichloromethane (20 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and was stirred for 12 h. Then the mixture was poured into a saturated solution of NaHCO, in water (50 ml). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extract was washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure. Further, pyridine was removed on a Kugelrohr apparatus at 40°C / 0.20 mbar. The residue was distilled on a Kugelrohr apparatus at 82°C / 1 mbar to give 1.31 g (82%) of the product as a clear colorless oil.

[0367] •H NMR (400 MHz, CDCl3): δ 4.43 (br. s., 1 H), 4.19 - 4.09 (m, 2 H), 4.09 - 3.98 (m, 1 H), 3.55 - 3.41 (m, 2 H), 3.36 (s, 3 H), 2.90 - 2.74 (m, 1 H), 1.82 - 1.39 (m, 6 H), 1.26 (t, J = 7.1 Hz, 3 H).

[0368] 13C NMR(101 MHz, CDCl3): δ 155.8, 70.3, 61.0, 58.7, 49.1, 39.8, 25.1, 25.0, 19.1, 14.5.

[0369] Example 26. Synthesis of ethyl 4-methoxypiperidine-l-carboxylate (D122)

[0370] 1. Ethyl 4-hydroxypiperidine-l -carboxylate

[0371] To a mixture of dichloromethane (150 ml) and a solution of NaHCO3(5.65 g, 67.2 mmol) in water (60 ml) a solution of piperidin-4-ol (4.00 g, 39.5 mmol) in dichloromethane (20 ml) was added dropwise at room temperature, followed by a solution of ethyl chloroformate (3.50 ml, 4.72 g, 43.5 mmol) in dichloromethane (10 ml) added dropwise at the same temperature. Then the obtained mixture was stirred for 12 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 5.81 g (85%) of the product as a yellowish oil, which then used without additional purification.

[0372] 1H NMR (400 MHz, CDCl3): δ 4.07 (q, J= 7.1 Hz, 2 H), 3.89 - 3.74 (m, 3 H), 3.10 - 3.00 (m, 2 H), 2.73 (s, 1 H), 1.87 - 1.74 (m, 2 H), 1.49 - 1.37 (m, 2 H), 1.21 (t, J= 7.1 Hz, 3 H).

[0373] 13C NMR (101 MHz, CDCl3): δ 155.5, 67.1, 61.2, 41.1, 33.8, 14.5.

[0374] 2. Ethyl 4-methoxypiperidine-1-carboxylate (D122)

[0375] To a suspension of NaH (prepared from 1.46 g of 60% wt. suspension in mineral oil, 36.4 mmol, washed with hexane) in THF (350 ml) methyl iodide (10.3 ml, 23.5 g, 165 mmol) was added dropwise at 0°C, followed by a solution of ethyl 4-hydroxypiperidine-1- carboxylate (5.73 g, 33.1 mmol) in THF (20 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and was stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 5.96 g (96%) of the product as a yellowish oil, which then used without additional purification.1H NMR (400 MHz, CDCl3): δ 4.05 (q, J = 7.1 Hz, 2 H), 3.75 - 3.65 (m, 2 H), 3.35 - 3.23 (m, 1 H), 3.28 (s, 3 H), 3.15 - 3.05 (m, 2 H), 1.83 - 1.70 (m, 2 H), 1.51 - 1.39 (m, 2 H), 1.19 (t, J= 7.1 Hz, 3 H).

[0376] 13C NMR (101 MHz, CDCl3): δ 155.3, 75.5, 61.0, 55.5, 40.9, 30.3, 14.5.

[0377] Example 27. Synthesis of ethyl isopropyl(2-methoxycyclopentyl)carbamate (D123)

[0378] 1. 2-(Isopropylamino)cyclopentan-l-ol

[0379] A mixture of cyclopentene oxide (10.4 ml, 10.0 g, 119 mmol), isopropylamine (20.4 ml, 14.1 g, 238 mmol) and LiBr (10.0 g, 115 mmol) in THF (250 ml) was stirred for 20 days at 50°C. Then the volatiles were removed under reduced pressure at 40°C / 200 mbar. The residue was diluted with water (200 ml) and extracted with dichloromethane (6 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure to give 6.06 g (36%) of the product as a white solid, which then used without additional purification.

[0380] 1H NMR (400 MHz, CDCl3): δ 3.80 (q, J = 6.7 Hz, 1 H), 2.96 - 2.83 (m, 2 H), 2.48 (br. s., 2 H), 2.07 - 1.96 (m, 1 H), 1.96 - 1.85 (m, 1 H), 1.76 - 1.58 (m, 2 H), 1.58 - 1.45 (m, 1 H), 1.30 - 1.16 (m, 1 H), 1.06 (d, J - 6.3 Hz, 3 H), 1.04 (d, J - 6.2 Hz, 3 H).

[0381] 13C NMR (101 MHz, CDCl3): δ 78.0, 64.0, 47.1, 32.2, 30.6, 23.9, 22.6, 20.1.

[0382] 2. Ethyl isopropyl(2-methoxycyclopentyl)carbamate (D123)

[0383] To a suspension of KH (prepared from 5.10 g of 30% wt. suspension in mineral oil, 38.1 mmol, washed with hexane) in diethyl ether (40 ml), a solution of 2- (isopropylamino)cyclopentan-l-ol (5.45 g, 38.1 mmol) in diethyl ether (80 ml) was added dropwise at 0°C, followed by a solution of methyl iodide (2.37 ml, 5.40 g, 38.1 mmol) in diethyl ether (40 ml) added drop wise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (20 ml). Then the residue was diluted with water (200 ml), the organic layer was separated and the aqueous layer was extracted with diethyl ether (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure at 40°C / 750 mbar to give 5.68 g (69%) of the oily mixture, that contained approximately 80% of the target product. This mixture was then used without additional purification.

[0384] To a mixture of dichloromethane (150 ml) and a solution of NaHCO3(5.16 g, 61.4 mmol) in water (60 ml) a solution of the above oily mixture (5.68 g) in dichloromethane (20 ml) was added dropwise at room temperature, followed by a solution of ethyl chloroformate (3.19 ml, 4.31 g. 39.7 mmol) in dichloromethane (10 ml) added dropwise at the same temperature. Then the obtained mixture was stirred for 12 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extract was washed with a solution of HC1 in water (pH 1, 50 ml), passed through a short pad of silica gel 60 (40-63 pm), which was additionally washed by dichloromethane (50 ml). The eluate was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 4.95 g (57%) of the product as a yellowish oil, which then used without additional purification.

[0385] 1H NMR (400 MHz, CDCl3): δ 4.17 (br. s., 1 H), 4.08 (q, J= 7.1 Hz, 2 H), 3.90 (br. s., 1 H), 3.51 - 3.35 (m, 1 H), 3.24 (s, 3 H), 2.07 - 1.65 (m, 4 H), 1.64 - 1.46 (m, 2 H), 1.22 (t, J = 7.1 Hz, 3 H), 1.14 (d, J= 6.8 Hz, 3 H), 1.08 (d, J = 6.8 Hz, 3 H).

[0386] 13C NMR (101 MHz, CDCl3): 155.3 (br. s.), 85.3 (br. s.), 61.4, 60.5, 57.2, 47.2, 30.1 , 29.5 (br. s.), 22.7, 21.0, 14.5.

[0387] Example 28. Synthesis of ethyl isopropyl(2-methoxycyclohexyl)carbamate (D124)

[0388] 1. 2-(lsopropylamino)cyclohexan-1-ol

[0389] A mixture of cyclohexene oxide (12.4 ml, 12.0 g, 122 mmol), isopropylamine (21.0 ml, 14.5 g, 245 mmol) and LiBr (10.0 g, 1 15 mmol) in THF (250 ml) was stirred for 8 days at 50°C. Then the volatiles were removed under reduced pressure at 40°C / 200 mbar. The residue was diluted with water (200 ml) and extracted with dichloromethane (6 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure to give 18.6 g (97%) of the product as a brownish solid, which then used without additional purification.

[0390] 1H NMR (400 MHz, CDCl3): δ 3.10 - 2.99 (m, 1 H), 2.98 - 2.87 (m, 1 H), 2.25 - 2.15 (m, 1 H), 2.10 - 1.95 (m, 2 H), 1.77 - 1.59 (m, 2 H), 1 .34 - 1.10 (m, 3 H), 1.03 (d, J = 6.3 Hz, 3 H), 0.97 (d, J = 6.1 Hz, 3 H), 0.93 - 0.78 (m, 1 H).

[0391] 13C NMR (101 MHz, CDCl3): δ 73.8, 60.6, 45.0, 33.0, 31.2, 25.3, 24.7, 24.3, 22.7.

[0392] 2. Ethyl isopropyl(2-methoxycyclohexyl)carbamate (D124)

[0393] To a suspension of KH (prepared from 8.50 g of 30% wt. suspension in mineral oil, 63.6 mmol, washed with hexane) in diethyl ether (70 ml), a solution of 2- (isopropylamino)cyclohexan-1-ol (10.0 g, 63.6 mmol) in diethyl ether (140 ml) was added dropwise at 0°C, followed by a solution of methyl iodide (3.96 ml, 9.02 g, 63.6 mmol) in diethyl ether (70 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (20 ml). Then the residue was diluted with water (200 ml), the organic layer was separated and the aqueous layer was extracted with diethyl ether (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure 40°C / 750 mbar to give 10.3 g (69%) of the oily mixture that contained approximately 80% of the target product. This mixture was then used without additional purification.

[0394] To a mixture of dichloromethane (250 ml) and a solution of NaHCO, (8.58 g, 102 mmol) in water (100 ml) a solution of the above oily mixture (10.3 g) in dichloromethane (30 ml) was added dropwise at room temperature, followed by a solution of ethyl chloroformate (5.31 ml, 7.17 g, 66.1 mmol) in dichloromethane (15 ml) added dropwise at the same temperature. Then the obtained mixture was stirred for 12 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 100 ml). The combined organic extract was washed with a solution of HC1 in water (pH 1, 100 ml), passed through a short pad of silica gel 60 (40-63 μm) which was additionally washed by dichloromethane (50 ml). The eluate was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 10 / 1 , v / v) to give 10.9 g (75%) of the product as an orange oil.

[0395] 1H NMR (400 MHz, CDCl3): δ 4.29 - 2.36 (br. s., 1 H), 4.29 - 4.01 (m, 2 H), 3.99 - 3.29 (m, 2 H), 3.26 (s, 3 H), 2.20 - 2.06 (m, 1 H), 1.87 - 1.42 (m, 4 H), 1.30 - 1 .00 (m, 12 H).

[0396] 13C NMR (101 MHz, CDCl3): δ 155.8 (br. s.), 79.0 (br. s.), 78.1 (br. s.), 60.3, 59.5 (br. s.), 59.1 (br. s.), 56.1 (br. s.), 46.5 (br. s.), 30.9 (br. s.), 29.9, 25.4, 24.3, 21.5, 20.9 (br. s.), 20.2, 14.6.

[0397] Example 29. Synthesis of ethyl 3-methoxypyrrolidine-1-carboxylate (D125)

[0398] 1. Ethyl 3-hydroxypyrrolidine-1-carboxylate

[0399] To a mixture of dichloromethane (150 ml) and a solution of NaHCO3(6.56 g, 78.1 mmol) in water (60 ml) a solution of pyrrolidin-3-ol (4.00 g, 45.9 mmol) in dichloromethane (20 ml) was added dropwise at room temperature, followed by a solution of ethyl chloroformate (4.06 ml, 5.48 g, 50.5 mmol) in dichloromethane (10 ml) added dropwise at the same temperature. Then the obtained mixture was stirred for 12 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO, and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 5.67 g (78%) of the product as a yellowish oil, which then used without additional purification.

[0400] 1H NMR (400 MHz, CDCl3): δ 4.44 - 4.32 (m, 1 H), 4.06 (q, J = 7.1 Hz, 2 H), 3.60 (s, 1 H), 3.53 - 3.26 (m, 4 H), 1.98 - 1.81 (m, 2 H), 1.20 (t, J= 7.1 Hz, 3 H).

[0401] 13C NMR (101 MHz, CDCl3): δ 155.4, 70.1 (br. s.), 61.0, 54.1, 43.7, 33.5, 14.6.

[0402] 2. Ethyl 3 -methoxypyrrolidine- 1 -carboxylate (D125) To a suspension of NaH (prepared from 1.57 g of 60% wt. suspension in mineral oil, 39.2 mmol, washed with hexane) in THF (350 ml) methyl iodide (11.1 ml, 25.3 g, 178 mmol) was added dropwise at 0°C, followed by a solution of ethyl 3-hydroxypyrrolidine-1- carboxylate (5.67 g, 35.6 mmol) in THF (20 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water (100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extract was dried over Na2SO4and the solvent was removed under reduced pressure. The residue was dried in vacuo to give 5.41 g (88%) of the product as a yellowish oil, which then used without additional purification.

[0403] 1H NMR (400 MHz, CDCl3): δ 4.09 (q, J = 7.1 Hz, 2 H), 3.95 - 3.84 (m, 1 H), 3.55 - 3.33 (m, 4 H), 3.28 (s, 3 H), 2.05 - 1.94 (m, 1 H), 1.94 - 1.81 (m, 1 H), 1.21 (t, J= 7.1 Hz, 3 H).

[0404] 13C NMR (101 MHz, CDCl3): δ 155.1, 79.3 (br. s.), 60.8, 56.4, 50.7, 43.7, 30.5 (br. s.), 14.7.

[0405] Comparative example C30.

[0406] In comparative example C30 2-ethoxyethyl methyl carbonate (EEMC) was synthesized as in Production Example 3 of patent US9243081B1 and then used as an internal donor.

[0407] Comparative example C31. Synthesis of N-ethyl-A-(2-methoxyethyl)benzamide (D56)

[0408] 1. N-(2-methoxyethyl)benzamide

[0409] To a solution of 2-methoxyethan-1-amine (5.25 g, 70.0 mmol) and triethylamine (19.5 ml, 14.2 g, 140 mmol) in dichloromethane (200 ml) a solution of benzoyl chloride (8.13 ml, 9.84 g, 70.0 mmol) in dichloromethane (30 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was poured into water (300 ml). The organic layer was separated and the aqueous layer was extracted with di chloromethane (3 x 100 ml). The combined organic extracts were washed with water (100 ml), dried over Na2SO4and the solvent was removed under reduced pressure to give 12.2 g (97%) of the product as a colorless solid, which then used without additional purification.

[0410] 1H NMR (400 MHz, CDCl3): δ 7.82 - 7.74 (m, 2 H), 7.52 - 7.46 (m, 1 H), 7.46 - 7.39 (m, 2 H), 6.60 (br. s., 1 H), 3.69 - 3.62 (m, 2 H), 3.58 - 3.53 (m, 2 H), 3.38 (s, 3 H).

[0411] 13C NMR (101 MHz, CDCl3): δ 167.5, 134.3, 131.2, 128.3, 126.8, 71.0, 58.6, 39.5.

[0412] 2. N-ethyl-N-(2-methoxyethyl) benzamide (D56)

[0413] To a suspension of NaH (prepared from 2.99 g of 60% suspension in mineral oil, 74.8 mmol, washed with hexane) in THF (200 ml) a solution of N-(2-methoxyethyl)benzamide (12.2 g, 68.0 mmol) in THF (25 ml) was added dropwise at 0°C, followed by a solution of ethyl iodide (6.00 ml, 11.7 g, 74.8 mmol) in THF (25 ml) added dropwise at the same temperature. The resulting mixture was allowed to warm to room temperature and stirred for 12 h. Then the mixture was quenched with water ( 100 ml) and THF was removed under reduced pressure. Then the residue was diluted with water (200 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic extracts were dried over Na2SO4and the solvent was removed under reduced pressure. The residue was purified by column chromatography (eluent: hexane / ethyl acetate = 10 / 1, v / v) to give 11.2 g (80%) of the product as a orange oil.

[0414] 1H NMR (400 MHz, CDCl3): δ 7.33 (s, 5 H), 3.73 - 3.12 (m, 9 H), 1.27 - 0.95 (m, 3 H).

[0415] 13C NMR (101 MHz, CDCl3): δ 171.6, 136.7, 128.9, 128.1, 126.5, 126.1, 70.6, 58.6, 47.9, 44.7, 44.2, 40.1, 13.8, 12.6.

[0416] Examples 32-56, comparative examples C57, C58. General procedure for the preparation of Ziegler Natta catalysts

[0417] A mixture of MgCT (1.10 g), phthalic anhydride (0.27 g), epichlorohydrin (1.81 ml), tributyl phosphate (2.29 ml) and toluene (16 ml) were placed in a round-bottom flask and stirred on a magnetic stirrer at a stirring speed of 400 rpm for 2 hours at 60°C. Then the mixture was cooled to -30°C and TiCL, (12.5 ml) was slowly added dropwise so that the temperature of the reaction mixture did not exceed -25°C. After the complete addition of TiCl4, the resulting mixture was warmed to room temperature and then stirred for 2 hours at 85°C. Then, the 1st portion (1.31 mmol) of an internal donor (prepared as described in examples 1-22, or a reference internal donor in comparative examples C23, C24) in toluene (5 ml) was added, and stirring was continued at this temperature for 1 hour. The resulting mixture was filtered while hot, the solid precipitate was suspended in toluene (15 ml). The second portion of the internal donor (0.69 mmol) in toluene (5 ml) was added to the resulting suspension, then, the resulting mixture was stirred for 1 h at 85 °C and filtered, the filter cake was washed with toluene (3 x 10 ml). The solid precipitate was suspended in a 10% (wt.) solution (22 ml) of TiCl4in toluene, then, the resulting suspension was kept under stirring for 1 hour at 95°C and again filtered while hot. The latter operation was repeated 3 times, with the difference that the suspension was kept at 110°C for half an hour under stirring. Then, the solid precipitate was washed with hexane (4 x 20 ml) and dried in vacuum. The powdery catalyst thus obtained was collected and stored in an inert atmosphere. The analytical data is presented in Table 1.

[0418] Examples 59-84, comparative examples C85-C87. General procedure for the propylene polymerization

[0419] Hexane was degassed by bubbling with argon and dried over molecular sieves 4Å. Polymerization grade propylene was used. Preparation of the catalyst slurry and introduction of hexane and catalyst slurry into the reactor was carried out in a glove box with a controlled nitrogen atmosphere (<1 ppm water, <1 ppm O2). Polymerizations were carried out in a 100 ml reactor equipped with a mechanical stirrer, a pressure gauge, a 200 bar rupture valve, a gas inlet, a PTFE insert and a unit for loading of a catalyst suspension, consisting of a 40 ml pressure vessel, which was filled with gas (propylene ) under a pressure exceeding the pressure in the reactor during polymerization, connected with a vessel for the catalyst suspension with a volume of 6.5 ml, connected to the reactor and was separated from the reactor and the pressure vessel by ball valves. The catalyst suspension was fed into the reactor by applying overpressure of propylene via successive opening of both ball valves for two seconds.

[0420] Catalyst powder (4.9-5.5 mg) and 1 ml of hexane were placed into a 4 ml glass vial equipped with a magnetic stirrer and a screw cap with a PTFE gasket. Next, the catalyst powder was suspended in hexane with stirring on a magnetic stirrer for 30 min. Then 60 equiv (per amount of titanium) of triethylaluminum, 12 equiv (per amount of titanium) of external donor (ED, Ph2Si(OMe)2), and 2.5 ml of hexane were added to the resulting suspension. Hexane (32 ml) and another 60 equiv (per amount of titanium) of triethylaluminum were placed in the reactor, then the reactor was closed. The catalyst powder slurry was then transferred to the vessel for the catalysts suspension connected with the reactor, the remaining volume of the vessel (about 2 ml) was filled with hexane. Nitrogen atmosphere in the reactor was replaced with propylene by repeated pressurizing the reactor with 10 bar of propylene and then venting the excessive pressure off. The reactor was then heated to a temperature of 60°C with stirring, and at this temperature hexane was saturated with propylene by supplying gaseous propylene through the gas inlet at a pressure of 5 bar. Then, the catalyst was fed into the reactor by overpressure (10 bar) of propylene. After that, polymerization was carried out for 20 to 40 minutes at a temperature of 70±1 °C. The polymerization was stopped venting the excessive pressure of propylene off. Then the reactor was opened, and the volatiles were removed in vacuum. The polymer thus obtained was dried in vacuum to constant weight and weighed. The activity was calculated as weight of the polymer (in kg) produced per one gram the catalyst per hour. The polymerization data is presented in Table 1.

[0421] Table 1

[0422] * comparative example; ** 2-ethoxyethyl methyl carbonate; *** N -ethyl- / V-(2- methoxyethyl)benzamide ;

[0423] PDI in examples 60, 81-84 and C86 was not determined

[0424] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.

Claims

CLAIMS1. A procatalyst for olefin polymerization comprising a titanium-containing compound, a magnesium-containing compound, a halogen, and an internal electron donor, which is a compound of Formula (I)whereinR1is selected from the group consisting of hydrogen, alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14,R2and R3are independently selected from the group consisting of alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14,L is a bridge selected fromwherein R4, R5, R6, R7, R8, R9are independently selected from the group consisting of hydrogen. alkyl or cycloalkyl,optionally substituted with one or more same or different substituents R14, R10, R11, R12, R13are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl, halogen, optionally substituted with one or more same or different substituents R14, wherein R14is independently selected from the group consisting of alkyl or cycloalkyl, optionally substituted aryl, halogen, and any of R1— R14may be linked together to form one or more saturated or unsaturated carbocyclic rings or saturated or unsaturated heterocyclic rings.

2. The procatalyst according to claim 1, wherein each of R1, R2, R3and R14is independently selected from the group consisting of: C1-C20linear or branched alkyl, preferably C1-C10linear or branched alkyl, more preferably C1-C6alkyl,C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl, and C6-C20aryl, preferably C6-C10aryl.

3. The procatalyst according to claim 1, wherein each of R4, R5, R6, R7, R8, R9, R10, R", R12and R13is independently selected from the group consisting of: C1-C20linear or branched alkyl, preferably C1-C10linear or branched alkyl, more preferably C1-C6alkyl,C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl.

4. The procatalyst according to claim 1, wherein each of R1, R2R3and R14is independently selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl and benzyl.

5. The procatalyst according to claim 1, wherein the internal electron donor is selected from the group consisting of: ethyl (2-methoxyethyl)carbamate, ethyl ethyl(2-methoxyethyl)carbamate, ethyl isobutyl(2-methoxyethyl)carbamate, ethyl benzyl(2-methoxyethyl)carbamate, ethyl phenyl(2-methoxyethyl)carbamate, ethyl isopropyl(2-methoxyethyl)carbamate, ethyl ethyl(3-methoxypropyl)carbamate, ethyl ethyl(2-methoxyphenyl)carbamate, ethyl (2-methoxyethyl)(2-methylcyclohexyl)carbamate,3-((tetrahydrofuran-2-yl)methyl)oxazolidin-2-one, ethyl ethyl((tetrahydrofuran-2-yl)methyl)carbamate, ethyl (2-isobutyl-2-(methoxymethyl)-4-methylpentyl)(methyl)carbamate, ethyl (4-methoxypentan-2-yl)(methyl)carbamate, ethyl 2-(2-methoxyethyl)piperidine-1-carboxylate, ethyl 2-(methoxymethyl)piperidine-1-carboxylate, ethyl 3-(methoxymethyl)piperidine-1-carboxylate, ethyl 3-methoxypiperidine-1-carboxylate, ethyl 3-methoxypyrrolidine-1-carboxylate, ethyl 4-methoxypiperidine-1-carboxylate, ethyl isopropyl(2-methoxycyclohexyl)carbamate, ethyl isopropyl(2-methoxycyclopentyl)carbamate, ethyl (2,6-diethylphenyl)(2-methoxyethyl)carbamate, ethyl (2-methoxyethyl)(o-tolyl)carbamate, ethyl ethyl(1-methoxybutan-2-yl)carbamate, isobutyl ethyl(2-methoxyethyl)carbamate, ethyl (S)-2-(methoxymethyl)pyrrolidine-1-carboxylate, ethyl isopropyl(2-methoxypropyl)carbamate,(S)-2-(methoxymethyl)indoline-1-carboxylate,3-(2-methoxyethyl)oxazolidin-2-one,3-(2-methoxyethyl)-1 ,3-oxazinan-2-one, ethyl 4-morpholinecarboxylate, and ethyl 8-methoxy-3,4-dihydroquinoline- 1(2H )-carboxylatc.

6. A method for the preparation of a procatalyst according to any one of claims 1 to 5, comprising the following steps:(a) contacting a magnesium-containing compound with a titanium-containing compound; and(b) adding to the mixture obtained in step (a) an internal electron donor, which is a compound of Formula (I),whereinR1is selected from the group consisting of hydrogen, alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14,R2and R1are independently selected from the group consisting of alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14,L is a bridge selected fromwherein R4, R5, R6, R7, R8, R9are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl. optionally substituted with one or more same or different substituents R14,R10, R11, R12, R13are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl, halogen, optionally substituted with one or more same or different substituents R14, wherein R14is independently selected from the group consisting of alkyl or cycloalkyl, optionally substituted aryl, halogen, and any of R1— R14may be linked together to form one or more saturated or unsaturated carbocyclic rings or saturated or unsaturated heterocyclic rings.

7. A catalyst system for olefin polymerization, comprising:(a) a procatalyst for olefin polymerization according to any one of claims 1 to 5, and(b) a co-catalyst.

8. The catalyst system according to claim 7, wherein the co-catalyst comprises an organoaluminum compound.

9. The catalyst system according to claim 8, wherein the organoaluminum compound is the compound of formulawhereinR19is independently selected from hydrocarbon groups having from 1 to 20 carbon atoms, X is a hydrogen atom or a halogen atom, and m is greater than 0 and equal to or less than 3.

10. The catalyst system according to claim 9, wherein the organoaluminum compound is selected from the group consisting of trialkylaluminums, trialkenylaluminums, dialkylaluminum halides, alkylaluminum sesquihalides, alkylaluminum dihalides, dialkylaluminum hydrides, and other partly hydrogenated alkylaluminums.1 1. The catalyst system according to claim 10, wherein the organoaluminum compound is selected from the group consisting of triethylaluminum, triisobutylaluminum, tri- / z- butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, triisoprenylaluminum, diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide, ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide, ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride, and propylaluminum dihydride.

12. The catalyst system according to any one of claims 8 to 11, wherein the organoaluminum compound is present in the catalyst system in such an amount that molar ratio of aluminum to titanium present in the procatalyst is from about 0.1 to about 1500, preferably from about 5 to about 1000, more preferably from about 10 to about 700, still more preferably from about 25 to about 400.

13. The catalyst system according to any one of claims 7 to 12, wherein the catalyst system further comprises an external electron donor.

14. The catalyst system according to claim 13, wherein the external electron donor is selected from the group consisting of silicon compounds, ethers, esters, amines, and heterocyclic compounds.

15. The catalyst system according to claim 13 or 14, wherein the external donor is a compound of formulawherein a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R16, R17, and R18are radicals with 1-18 carbon atoms optionally containing heteroatoms.

16. The catalyst system according to claim 15, wherein a is 1, b is 1, c is 2, at least one of R16and R17is selected from branched alkyl, cycloalkyl, or aryl groups with 3-10 carbon atoms optionally containing heteroatoms, and R18is a C1-C10alkyl group, preferably methyl.

17. The catalyst system according to claim 16, wherein the external electron donor is selected from the group consisting of methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, (2- ethylpiperidinyl)-tert-butyldimethoxysilane, (2-ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n- propyl)dimethoxysilane, and N,N-diethylaminotriethoxysilane.

18. The catalyst system according to claim 15, wherein a is 0, c is 3, R17is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R18is methyl.

19. The catalyst system according to claim 15, wherein the external electron donor is selected from the group consisting of cyclohexyltrimethoxysilane, tert- butyltrimethoxysilane, and hexyltrimethoxysilane.

20. The catalyst system according to any one of claims 13 to 19, wherein the external electron donor is used in such an amount to give a molar ratio between the co-catalyst and said external electron donor of from 0.1 to 600, preferably from 1 to 300, and more preferably from 3 to 100.

21. A method for the preparation of a catalyst system for olefin polymerization, comprising contacting the procatalyst according to any one of claims 1 to 5 with a co- catalyst.

22. The method according to claim 21 , wherein the procatalyst is contacted with the co- catalyst in the presence of an external electron donor.

23. A method for olefin (co)polymerization, comprising contacting at least one olefin monomer with the catalyst system according to any one of claims 7 to 20.

24. Use of the compound of Formula (I)whereinR1is selected from the group consisting of hydrogen, alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14,R2and R3are independently selected from the group consisting of alkyl or cycloalkyl, aryl, optionally substituted with one or more same or different substituents R14,L is a bridge selected fromwherein R4, R5, R6, R7, R8, R9are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl, optionally substituted with one or more same or different substituents R14, R10, R11, R12, R13are independently selected from the group consisting of hydrogen, alkyl or cycloalkyl, halogen, optionally substituted with one or more same or different substituents R14, wherein R14is independently selected from the group consisting of alkyl or cycloalkyl, optionally substituted aryl, halogen, and any of R1— R14may be linked together to form one or more saturated or unsaturated carbocyclic rings or saturated or unsaturated heterocyclic rings, as an internal electron donor of a catalyst for olefin polymerization.

25. The use according to claim 24, wherein each of R1, R~ R’ and R14is independently selected from the group consisting of:C1-C20linear or branched alkyl, preferably C1-C10linear or branched alkyl, more preferably C1-C6alkyl,C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C1-C6cycloalkyl, andC6-C20aryl, preferably C6-C10aryl.

26. The use according to claim 24, wherein each of R4, R5, R6, R", R8, R’, R10, R11, R12, and R13is independently selected from the group consisting of: C1-C20linear or branched alkyl, preferably C1-C10linear or branched alkyl, more preferably C1-C6alkyl, C3-C20cycloalkyl, preferably C3-C10cycloalkyl, more preferably C3-C6cycloalkyl.

27. The use according to claim 24, wherein each of R1, R2R3and R14is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl and benzyl.

28. The use according to any one of claims 24 to 27, wherein the compound of Formula (I) is selected from the group consisting of: ethyl (2-methoxyethyl)carbamate, ethyl ethyl(2-methoxyethyl)carbamate, ethyl isobutyl(2-methoxyethyl)carbamate, ethyl benzyl(2-methoxyethyl)carbamate, ethyl phenyl(2-methoxyethyl)carbamate, ethyl isopropyl(2-methoxyethyl)carbamate, ethyl ethyl(3-methoxypropyl)carbamate, ethyl ethyl(2-methoxyphenyl)carbamate, ethyl (2-methoxyethyl)(2-methylcyclohexyl)carbamate, 3-((tetrahydrofuran-2-yl)methyl)oxazolidin-2-one, ethyl ethyl((tetrahydrofuran-2-yl)methyl)carbamate, ethyl (2-isobutyl-2-(methoxymethyl)-4-methylpentyl)(methyl)carbamate, ethyl (4-methoxypentan-2-yl)(methyl)carbamate, ethyl 2-(2-methoxyethyl)piperidine-1-carboxylate, ethyl 2-(methoxymethyl)piperidine-1-carboxylate, ethyl 3-(methoxymethyl)piperidine-1-carboxylate, ethyl 3-methoxypiperidine-1-carboxylate, ethyl 3 -methoxypyrrolidine-1-carboxylate,ethyl 4-methoxypiperidine-1-carboxylate, ethyl isopropyl(2-methoxycyclohexyl)carbamate, ethyl isopropyl(2-methoxycyclopentyl)carbamate, ethyl (2,6-diethylphenyl)(2-methoxyethyl)carbamate, ethyl (2-methoxyethyl)(o-tolyl)carbamate, ethyl ethyl(1-methoxybutan-2-yl)carbamate, isobutyl ethyl(2-methoxyethyl)carbamate, ethyl (S)-2-(methoxymethyl)pyrrolidine-1-carboxylate, ethyl isopropyl(2-rnethoxypropyl)carbamate,(S)-2-(methoxymethyl)indoline-1-carboxylate,3-(2-methoxyethyl)oxazolidin-2-one,3-(2-methoxyethyl)-1,3-oxazinan-2-one, ethyl 4-morpholinecarboxylate, and ethyl 8-methoxy-3,4-dihydroquinoline-1(2H)-carboxylate.

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