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WO2019030059A1 - Bissilylaminosilyl-functionalized conjugated dienes and methods for their preparation - Google Patents

Bissilylaminosilyl-functionalized conjugated dienes and methods for their preparation Download PDF

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Publication number
WO2019030059A1
WO2019030059A1 PCT/EP2018/070768 EP2018070768W WO2019030059A1 WO 2019030059 A1 WO2019030059 A1 WO 2019030059A1 EP 2018070768 W EP2018070768 W EP 2018070768W WO 2019030059 A1 WO2019030059 A1 WO 2019030059A1
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Prior art keywords
group
formula
conjugated diene
carbon atoms
myrcene
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Application number
PCT/EP2018/070768
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French (fr)
Inventor
Maria SIOLEK
Radoslaw KOZAK
Pawel WEDA
Robert BOGACZ
Tomasz SKROK
Dawid BARTUS
Original Assignee
Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna
Synthos S.A.
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Publication of WO2019030059A1 publication Critical patent/WO2019030059A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms

Definitions

  • the present invention relates to bissilylaminosilyl-functional- ized conjugated dienes and to methods for their preparation.
  • conjugated diene monomers A variety of conjugated diene monomers is known that can be used in the production of synthetic rubbers. However, there is a need in the art for further conjugated diene monomers that can be used in advantageous polymerization processes, or that confer advantageous properties to the rubbers prepared from such con ⁇ jugated diene monomers.
  • EP 3 064 546 Al teaches the use of vinylsilanes in the production of rubbers.
  • EP 2 857 446 Al teaches a conjugated diene polymer derived from conjugated diene, a monomer unit V 1 -S 1 , and a monomer unit V 2 -A 2 , where V 1 and V 2 each represent a hydrocarbyl group containing a polymerizable carbon carbon double bond, S 1 repre ⁇ sents a substituted silyl group, and A 2 is an amino group or a nitrogen-containing heterocycle group.
  • US 3,413,364 B discloses a process for the selective production of myrcenyl halides by reacting myrcene with hydrogen halides in the presence of certain Lewis acids and/or a high surface area catalyst.
  • the myrcenyl halide produced is 2-halo-2-methyl-6- methylene-7-octene .
  • hydrohalogenation results in that the isolated double bond as present in myrcene is not retained.
  • U.S. 4,754,087 B teaches the hydrohalogenation of conjugated dienes.
  • US 4,665,244 B discloses 3-chloro-myrcene as starting material in the preparation of a hexadecane derivative, for the synthesis of tocopherol and tocopherol acetate.
  • TCCA trichloroisocyanuric acid
  • EP 0 872 463 Al teaches the preparation of substituted 1-chlo- roalkenes using TCCA.
  • the substituted 1-chloroalkenes (which have one carbon-carbon double bond only, and are enol alkyl or silyl ethers, or enol carboxylic acid esters, or enamines) can be used in the preparation of alpha-chloroketones , which are useful as fungicides.
  • WO2016/162473 Al and WO2016/162528 Al Al disclose aminosilyl- functionalized styrenes and methods for their preparation, as well as the use of the styrene derivatives in the preparation of a copolymer thereof.
  • EP 3 159 346 Al teaches aminosilane-functionalized diene com ⁇ pounds that are useful as modifying monomers in the polymeriza ⁇ tion of conjugated diene monomers, optionally together with ar ⁇ omatic vinyl monomers, thus producing polymers, specifically elastomeric polymers, which can be used in rubber articles such as tires.
  • Exemplified are aminosilylmethyl derivatives of (oth ⁇ erwise unsubstituted) 1 , 3-butadiene, and these derivatives are synthesized using chloroprene. Synthetic methods involving chlo- roprene are often considered undesirable because the substance is highly flammable and is consequently strictly regulated. Also, chloroprene is prone to self-polymerization .
  • conjugated diene monomers that are suitable in the production of synthetic rubbers.
  • conjugated diene monomers should be based on easily accessible starting materials, and via simple synthetic routes.
  • conjugated dienes having at least 10 carbon atoms such as terpenes (e.g. monoterpenes, for instance myrcene)
  • terpenes e.g. monoterpenes, for instance myrcene
  • the functionalized conjugated dienes are easily accessible from the starting conjugated dienes by chlo- rination, namely using a chlorinating agent comprising tri- chloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of dichloroisocyanuric acid, or a mixture thereof.
  • the starting conjugated dienes are readily available substances.
  • the chlorinated intermediates do not have the disadvantages that chloroprene is associated with.
  • N-chloro- or N-bromosuccinimide Treatment with N-chloro- or N-bromosuccinimide in the pres ⁇ ence of catalytic amounts of H 2 SO 4 .
  • N-bromosuccinimide gives a poor yield of the desired product (20%) .
  • N-chlorosuc- cinimide has poorer solubility in organic solvents, and a lower amount of active chlorine, as compared to the chlorinating agents as used according to the present invention, in particular TCCA.
  • (la) (lb) (Ic) wherein R is a linear or branched, saturated or unsaturated hydrocarbylene group, and the starting conjugated diene of for ⁇ mula (la), (lb), (Ic) has at least 10 carbon atoms, with a chlorinating agent comprising trichloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of dichloroiso- cyanuric acid, or a mixture thereof.
  • a chlorinating agent comprising trichloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of dichloroiso- cyanuric acid, or a mixture thereof.
  • the present invention relates to the functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb) , (IIIc) .
  • R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
  • a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR 6 , and a group SiR 7 R 8 ,
  • R 2 , R 3 , R 6 , R 7 , R 8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
  • R 4 and R 5 can be the same or different, and each R 4 and R 5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comprises reacting, under Grignard conditions, a con ⁇ jugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
  • Y is selected from chlorine, bromine, and iodine atoms
  • R is a linear or branched, saturated or unsaturated hydro ⁇ carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
  • R 1 is selected from
  • a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR 6 , and a group SiR 7 R 8 ,
  • R 2 , R 3 , R 6 , R 7 , R 8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
  • R 4 and R 5 can be the same or different, and each R 4 and R 5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comp
  • Y 1 and Y 2 are independently selected from chlorine, bromine, and iodine atoms, and preferably Y 1 and Y 2 are each chlorine atoms, to result in a compound of formula (IXa), (IXb), (IXc)
  • M is an alkali metal selected from lithium, sodium and potassium, and M is preferably sodium.
  • the functionalized conjugated diene of formula (Ilia), (Illb) , (IIIc) can be used especially for the functionalization of poly- butadiene rubbers, such as rubbers as obtained by anionic polymerization of butadienes using an organolithium initiator (Li-BR) , or by coordination polymerization using a Ziegler-Natta type of catalyst (e.g. neodymium, Nd-BR) , or in the production of solution styrene-butadiene rubber (SSBR) .
  • organolithium initiator Li-BR
  • a Ziegler-Natta type of catalyst e.g. neodymium, Nd-BR
  • SSBR solution styrene-butadiene rubber
  • the method for the preparation of a conjugated diene chloride comprises chlorinating a starting conjugated diene selected from the group of co
  • (la) (lb) (Ic) wherein R is a linear or branched, saturated or unsaturated hydrocarbylene group, and the starting conjugated diene of for ⁇ mula (la), (lb), (Ic) has at least 10 carbon atoms, with a chlorinating agent comprising trichloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of dichloroiso- cyanuric acid, or a mixture thereof.
  • the starting conjugated diene is a terpene, or is 4, 8-dimethyl-l, 3, 7-nonatriene .
  • the starting conjugated diene of formula (la), (lb), (Ic) further contains one or more additional double bonds. More preferably, the starting conjugated diene contains one addi ⁇ tional double bond, i.e. is a triene.
  • the starting conjugated diene preferably further contains, in addition to the conjugated double bonds as shown in formulae (la), (lb), (Ic), one or more (and preferably one) additional double bond.
  • the chlorinating agents as used do not hydrohalogenate this additional double bond. It was found that, if one were to hydrohalogenate this additional double bond in myrcene, the corresponding functionalised conjugated dienes are inactive for SSBR, Li-BR and ZN-BR (such as Nd-BR) type of applications.
  • the terpene starting material for the prep ⁇ aration of the chlorinated intermediate is selected from mono- terpenes, sesquiterpenes, and diterpenes.
  • the ter ⁇ pene is a monoterpene, such as myrcene or ocimene.
  • the myrcene starting material for the method according to the first aspect is selected from -myrcene and ⁇ -myrcene, most preferably, the myrcene is ⁇ -myrcene.
  • Monoterpenes are dimers of isoprenoid precursors, and myrcene is one of the most important ones because it is a relevant precursor to many terpenes.
  • Myrcene is a monoterpene with a highly active diene structure. It is used in a variety of industrial processes. For example, the technical syntheses of flavors such as menthol, geraniol, nerol, and linalool typically start from myrcene.
  • myrcene has been used in organic chemistry for a long time, yielding products for different applications: polymers, pharmaceuticals, insect repellents, flavors and fragrances, vit ⁇ amins, and biodegradable surfactants.
  • myrcene is a rela ⁇ tively inexpensive and environmentally friendly starting mate ⁇ rial .
  • Examples for the starting conjugated dienes are the following monoterpenes: myrcenes, or 3, 7-dimethyl-l, 3, 7-octatriene ((E)- -ocimene) , (Z) -3, 7-dimethyl-l, 3, 6-octatriene ( (Z) - ⁇ -ocimene) , (E) -3, 7 -dimethyl- 1, 3, 6-octatriene ( (E) - ⁇ -ocimene) , or 2,6-dime- thyl-2 , 4 , 6-octatriene (allo-ocimene) .
  • 4, 8-dimethyl-l, 3, 7-nonatriene is used as a start ⁇ ing conjugated diene.
  • the chlorination of myrcene may thus proceed as follows:
  • the myrcene chloride produced is most preferably 3-chloro- - myrcene having the following formula (II)
  • the reaction is preferably performed in a solvent selected from ethyl acetate, cyclohexane or acetone, or a mixture thereof.
  • a solvent selected from ethyl acetate, cyclohexane or acetone, or a mixture thereof.
  • the best result due to the best solubility of TCCA was obtained in acetone. Consequently, the most preferred solvent to be used is acetone .
  • any additional un- saturation e.g. one or more double bonds
  • the chlorinating agents result in substitution of a hydrogen atom with a chlorine atom, rather than addition of hydrochloric acid and loss of the additional unsaturation .
  • the chlorinating agent is preferably selected from trichloroisocyanuric acid, di- chloroisocyanuric acid, and mixtures thereof. Most preferably, the chlorinating agent is trichloroisocyanuric acid.
  • the conjugated diene chloride is an intermediate. It is prefer ⁇ ably used in a method which produces the functionalized conju ⁇ gated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
  • R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
  • hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR 6 , and a group SiR 7 R 8 ,
  • R 2 , R 3 , R 6 , R 7 , R 8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
  • R 4 and R 5 can be the same or different, and each R 4 and R 5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms.
  • the method in one embodiment comprises reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
  • Y is selected from chlorine, bromine, and iodine atoms.
  • the Grignard conditions preferably comprise reacting in the presence of magnesium metal, in an ether solvent (such as diethyl ether, or tetrahydrofurane, THF), with a reaction initiator.
  • a reaction initiator such as diethyl ether, or tetrahydrofurane, THF
  • Preferred reaction initiators are elemental iodine, diisobutyl- aluminium hydride (DIBAH), or 1 , 2-dibromoethane .
  • the compound of formula (Ila), (lib), or (lie) can in one embodiment be reacted with magnesium metal first, to prepare the corresponding magnesium Grignard compound, which is in a subsequent step reacted with the compound of formula (IV) .
  • the magnesium Gri ⁇ gnard compound of the compound of formula (Ila), (lib), or (lie) is generated in situ and reacted with the compound of formula (IV) .
  • the invention consequently in one embodiment relates to the in situ Grignard reaction of chloromyrcene with 1- [ ⁇ N, N-bis ( trime- thylsilylamino) ⁇ (dimethylsilyl ) ] -2- ⁇ chlorodimethylsilyl ⁇ - ethane, as follows:
  • R is a linear or branched, saturated or unsaturated hydro ⁇ carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
  • a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR 6 , and a group SiR 7 R 8 , - R 2 , R 3 , R 6 , R 7 , R 8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
  • R 4 and R 5 can be the same or different, and each R 4 and R 5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, comprises
  • Y 1 and Y 2 are independently selected from chlorine, bromine, and iodine atoms, and preferably Y 1 and Y 2 are each chlorine atoms, to result in a compound of formula (IXa), (IXb), (IXc)
  • the invention also relates to functionalized conjugated dienes selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
  • a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR 6 , and a group SiR 7 R 8 ,
  • R 2 , R 3 , R 6 , R 7 , R 8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
  • R 4 and R 5 can be the same or different, and each R 4 and R 5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms.
  • R 1 is ( a) -(CH 2 ) m -, wherein m represents an integer from 1 to 12; or
  • R 1 of the functionalized conjugated diene is (iii)b) - (SiR 7 R 8 CH 2 CH 2 ) - .
  • R 2 , R 3 , R 6 , R 7 , and R 8 are the same or different and represent C3 ⁇ 4 or C 6 H 5 , preferably R 2 , R 3 , R 6 , R 7 , and R 8 all represent CH 3 .
  • R 4 and R 5 all represent C3 ⁇ 4 .
  • the starting con ⁇ jugated diene selected from the group of compounds of formula
  • (la), (lb), (Ic) is selected from terpenes and 4 , 8-dimethyl- 1, 3, 7-nonatriene .
  • the terpene is selected from myr- cene and ocimene, in particular, the terpene is myrcene selected from -myrcene and ⁇ -myrcene.
  • Preferred functionalized conjugated dienes according to the third aspect of the invention are myrcene derivatives of formula (VI), (VII), or (VIII)
  • the myrcene derivative according to the third aspect of the invention is of formula (Via) , (Vila) , or (Villa)
  • a method for the preparation of a conjugated diene chloride comprising chlorinating a starting conjugated diene selected from the group of compounds of formula (la), (lb), (Ic)
  • the starting conjugated diene of formula (la), (lb), or (Ic) further contains one or more additional double bonds, preferably wherein the starting conjugated diene contains one additional double bond, more preferably wherein the starting conjugated diene is a terpene or is 4, 8-dimethyl-l, 3, 7-nonatriene .
  • the terpene is selected from monoterpenes , sesquiterpenes, and diterpenes, preferably wherein the terpene is a monoterpene, more preferably wherein the monoterpene is selected from myr- cene and ocimene, in particular wherein the myrcene is selected from -myrcene and ⁇ -myrcene.
  • the method of paragraph 3 wherein the myrcene is ⁇ -myrcene.
  • the method of paragraph 4 wherein the myrcene chloride pro ⁇ quizd is 3-chloro-a-myrcene having the following formula (II)
  • the chlorinating agent is selected from trichloroisocyanuric acid, dichloroisocyanuric acid, and mixtures thereof, preferably wherein the chlorinating agent is trichloroisocy ⁇ anuric acid.
  • R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
  • a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR 6 , and a group SiR 7 R 8 ,
  • R 2 , R 3 , R 6 , R 7 , R 8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and R 4 and R 5 can be the same or different, and each R 4 and R 5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comprising reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
  • Y is selected from chlorine, bromine, and iodine at ⁇ oms .
  • R is a linear or branched, saturated or unsaturated hydro ⁇ carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
  • R 1 is selected from
  • a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR 6 , and a group SiR 7 R 8 ,
  • R 2 , R 3 , R 6 , R 7 , R 8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
  • R 4 and R 5 can be the same or different, and each R 4 and R 5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comprising
  • Y 1 and Y 2 are independently selected from chlorine, bromine, and iodine atoms, and preferably Y 1 and Y 2 are each chlorine atoms, to result in a compound of formula (IXa), (IXb), (IXc)
  • a functionalized conjugated diene selected from the group compounds of formula (Ilia), (Illb), (IIIc)
  • a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR 6 , and a group SiR 7 R 8 ,
  • R 2 , R 3 , R 6 , R 7 , R 8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
  • R 4 and R 5 can be the same or different, and each R 4 and R 5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms.
  • R 1 is (iii) a) -(CH 2 ) m -, wherein m represents an integer from 1 to 12; or
  • R 2 , R 3 , R 6 , R 7 , and R 8 are the same or different and represent CH 3 or Celi 5 , preferably wherein R 2 , R 3 , R 6 , R 7 , and R 8 all represent C3 ⁇ 4 .
  • the myrcene derivative is of formula (Via) , (Vila), or (Villa)
  • Chloromyrcene as obtained according to Example 1 was positively tested in the Grignard reaction.
  • GC-FID chromatogram showed myr- cene and its isomers, two unknown impurities and the function- alized conjugated diene monomer of the invention (three iso ⁇ mers) .
  • reaction mixture was slowly added to a round-bottom flask containing a 20% solution of bis (trimethylsilyl) amine in THF (or toluene). The resultant mixture was stirred for 2 h. After completion of the reaction, solvent was evaporated, and the obtained solid was filtered, yielding a yellow oil.

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Abstract

The invention relates to bissilylaminosilyl-functionalized conjugated dienes of formula (IlIa), (Illb) or (IIIc) (formula IIIa, b, c) and to methods for their preparation. The conjugated dienes of formula (Ilia), (Illb) or (IIIc) are based on terpenes or 4,8-dimethyl-1, 3, 7-nonatriene as starting materials.

Description

Bissilylaminosilyl-functionalized conjugated dienes and
methods for their preparation
The present invention relates to bissilylaminosilyl-functional- ized conjugated dienes and to methods for their preparation.
A variety of conjugated diene monomers is known that can be used in the production of synthetic rubbers. However, there is a need in the art for further conjugated diene monomers that can be used in advantageous polymerization processes, or that confer advantageous properties to the rubbers prepared from such con¬ jugated diene monomers.
State of the art
P. P. Choudhury and M. E. Welker (Molecules 2015, 20, 16892- 16907) report the preparation of 2-silicon-substituted 1,3- dienes via Grignard chemistry. The authors further report the use of the 2-silicon-substituted 1,3-dienes in one pot metathe- sis/Diels-Alder reactions in regio- and diastereoselective fash¬ ions .
EP 3 064 546 Al teaches the use of vinylsilanes in the production of rubbers. EP 2 857 446 Al teaches a conjugated diene polymer derived from conjugated diene, a monomer unit V1-S1, and a monomer unit V2-A2, where V1 and V2 each represent a hydrocarbyl group containing a polymerizable carbon carbon double bond, S1 repre¬ sents a substituted silyl group, and A2 is an amino group or a nitrogen-containing heterocycle group.
US 3,413,364 B discloses a process for the selective production of myrcenyl halides by reacting myrcene with hydrogen halides in the presence of certain Lewis acids and/or a high surface area catalyst. The myrcenyl halide produced is 2-halo-2-methyl-6- methylene-7-octene . Hence, hydrohalogenation results in that the isolated double bond as present in myrcene is not retained. Likewise, U.S. 4,754,087 B teaches the hydrohalogenation of conjugated dienes.
K. Ziegler et al . (Anal Chem. 1942, 551, 80) report the allylic halogenation of cyclohexene, which produced a mixture of prod¬ ucts. A. Behr and L. Johnen (ChemSusChem 2009, 2, 1072-1095) review the allylic chlorination of the isolated double bond of myrcene, with N-chlorosuccinimide and catalytic amounts of H2SO4 (DD245657, 60 % yield), with phenylselenyl chloride as catalyst (J. A. Tunge, S. R. Mellegaard, Org. Lett. 2004, 6, 1205, 69 % yield), with sulfuryl chloride (M. Bullard, G. Balme, J. Gore, Tetrahedron Lett. 1989, 30, 5767, 69 %) , or with chlorine gas (G. Mignani, J. P. Grass, P. Chabardes, D. Morel, Tetrahedron Lett. 1992, 33, 495, 87 %) .
US 4,665,244 B discloses 3-chloro-myrcene as starting material in the preparation of a hexadecane derivative, for the synthesis of tocopherol and tocopherol acetate.
U. Tilstam and H. Weinmann (Organic Process Research & Develop¬ ment 2002, 6, 384-393) teach that trichloroisocyanuric acid (TCCA) is a safe and efficient chlorination and oxidation reagent. However, TCCA is mainly used for the disinfection of swimming pools, the non-shrinking treatment of wool, and the cleaning and sterilizing of bathrooms. It is also used in laundry bleach as well as for removing oil and protein from stainless steel.
EP 0 872 463 Al teaches the preparation of substituted 1-chlo- roalkenes using TCCA. The substituted 1-chloroalkenes (which have one carbon-carbon double bond only, and are enol alkyl or silyl ethers, or enol carboxylic acid esters, or enamines) can be used in the preparation of alpha-chloroketones , which are useful as fungicides.
WO2016/162473 Al and WO2016/162528 Al Al disclose aminosilyl- functionalized styrenes and methods for their preparation, as well as the use of the styrene derivatives in the preparation of a copolymer thereof.
EP 3 159 346 Al teaches aminosilane-functionalized diene com¬ pounds that are useful as modifying monomers in the polymeriza¬ tion of conjugated diene monomers, optionally together with ar¬ omatic vinyl monomers, thus producing polymers, specifically elastomeric polymers, which can be used in rubber articles such as tires. Exemplified are aminosilylmethyl derivatives of (oth¬ erwise unsubstituted) 1 , 3-butadiene, and these derivatives are synthesized using chloroprene. Synthetic methods involving chlo- roprene are often considered undesirable because the substance is highly flammable and is consequently strictly regulated. Also, chloroprene is prone to self-polymerization .
Accordingly, it was an object of the invention to provide conjugated diene monomers that are suitable in the production of synthetic rubbers. These conjugated diene monomers should be based on easily accessible starting materials, and via simple synthetic routes.
It has now surprisingly been found in accordance with the present invention that conjugated dienes having at least 10 carbon atoms, such as terpenes (e.g. monoterpenes, for instance myrcene) , are suitable starting materials for the preparation of functional- ized conjugated dienes. The functionalized conjugated dienes are easily accessible from the starting conjugated dienes by chlo- rination, namely using a chlorinating agent comprising tri- chloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of dichloroisocyanuric acid, or a mixture thereof. The starting conjugated dienes are readily available substances. The chlorinated intermediates do not have the disadvantages that chloroprene is associated with.
In the literature, a few methods for selective chlorination are reported :
1. Treatment with N-chloro- or N-bromosuccinimide in the pres¬ ence of catalytic amounts of H2SO4. However, N-bromosuccinimide gives a poor yield of the desired product (20%) . N-chlorosuc- cinimide has poorer solubility in organic solvents, and a lower amount of active chlorine, as compared to the chlorinating agents as used according to the present invention, in particular TCCA.
2. With phenylselenyl chloride as catalyst. However, this chlorinating agent is toxic.
3. With sulfuryl chloride (in methylene chloride as a solvent) . In this reaction, 4 equivalents of a2C03 are used in order to react with HC1 byproduct. Hence, this type of reaction will generate a large amount of waste. Moreover, SO2CI2 reacts less selectively than TCCA. Also, the solvent is less environmentally friendly than the solvents as used in accordance with the present invention, such as acetone. Finally, SO2CI2 is toxic and corro¬ sive .
4. Chlorine gas. Again, this chlorinating agent is very toxic. That any additional unsaturation (e.g. further one or more double bonds), as may be present in the starting conjugated dienes (e.g. terpenes) , may be retained according to the present invention was surprising and expands on the teaching of EP 0 872 463 Al .
Accordingly, presently disclosed is to a method for the prepa¬ ration of a conjugated diene chloride comprising chlorinating a starting conjugated diene selected from the group of compounds of formula (la) (lb), (Ic)
Figure imgf000006_0001
(la) (lb) (Ic) , wherein R is a linear or branched, saturated or unsaturated hydrocarbylene group, and the starting conjugated diene of for¬ mula (la), (lb), (Ic) has at least 10 carbon atoms, with a chlorinating agent comprising trichloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of dichloroiso- cyanuric acid, or a mixture thereof.
The present invention relates to the functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb) , (IIIc) .
Furthermore, and in one embodiment of a method for the prepara¬ tion of a functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000007_0001
(Ilia) (Illb) (IIIc) wherein
R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
Figure imgf000007_0002
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms ,
- R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
- R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comprises reacting, under Grignard conditions, a con¬ jugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
Figure imgf000008_0001
Ha li with a compound of formula (IV)
Figure imgf000008_0002
wherein Y is selected from chlorine, bromine, and iodine atoms
Furthermore, and in another embodiment of a method for the prep¬ aration of a functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000009_0001
(Ilia) (Illb) (Hie) wherein
R is a linear or branched, saturated or unsaturated hydro¬ carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
Figure imgf000009_0002
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms ,
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comp
A) reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
Figure imgf000010_0001
with a compound of formula (V)
Figure imgf000010_0002
wherein Y1 and Y2 are independently selected from chlorine, bromine, and iodine atoms, and preferably Y1 and Y2 are each chlorine atoms, to result in a compound of formula (IXa), (IXb), (IXc)
Figure imgf000011_0001
(IXa) (IXb) (IXc)
and
B) reacting the compound of formula (IXa), (IXb), (IXc) with a bissilylamide of formula (X)
+
Figure imgf000011_0002
wherein M is an alkali metal selected from lithium, sodium and potassium, and M is preferably sodium.
The functionalized conjugated diene of formula (Ilia), (Illb) , (IIIc) can be used especially for the functionalization of poly- butadiene rubbers, such as rubbers as obtained by anionic polymerization of butadienes using an organolithium initiator (Li-BR) , or by coordination polymerization using a Ziegler-Natta type of catalyst (e.g. neodymium, Nd-BR) , or in the production of solution styrene-butadiene rubber (SSBR) . Further details re¬ garding this use of the functionalized conjugated diene of for¬ mula (Ilia) , (Illb) , (IIIc) are given in the international ap¬ plication entitled "Bissilylaminosilyl-functionalized conju¬ gated dienes and their use in the production of rubbers" filed on even date' herewith (attorney reference SH 1511-03WO, PCT/EP2018/070796) , which international application is incorpo¬ rated herein in its entirety and which international application claims priority from 1) EP17201732.9 filed 14 November 2017 (which is also the filing date of EP17201702.2, from which the present application claims priority) , and
2) EP 17461581.5 filed August 8, 2017 (which is also the filing date of EP17461580.7, from which the present application also claims priority) .
Detailed description
The method for the preparation of a conjugated diene chloride comprises chlorinating a starting conjugated diene selected from the group of co
Figure imgf000012_0001
(la) (lb) (Ic) , wherein R is a linear or branched, saturated or unsaturated hydrocarbylene group, and the starting conjugated diene of for¬ mula (la), (lb), (Ic) has at least 10 carbon atoms, with a chlorinating agent comprising trichloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of dichloroiso- cyanuric acid, or a mixture thereof. The starting conjugated diene is a terpene, or is 4, 8-dimethyl-l, 3, 7-nonatriene .
Preferably, the starting conjugated diene of formula (la), (lb), (Ic) further contains one or more additional double bonds. More preferably, the starting conjugated diene contains one addi¬ tional double bond, i.e. is a triene.
As mentioned, the starting conjugated diene preferably further contains, in addition to the conjugated double bonds as shown in formulae (la), (lb), (Ic), one or more (and preferably one) additional double bond. Surprisingly, the chlorinating agents as used do not hydrohalogenate this additional double bond. It was found that, if one were to hydrohalogenate this additional double bond in myrcene, the corresponding functionalised conjugated dienes are inactive for SSBR, Li-BR and ZN-BR (such as Nd-BR) type of applications.
It is preferred that the terpene starting material for the prep¬ aration of the chlorinated intermediate is selected from mono- terpenes, sesquiterpenes, and diterpenes. Preferably, the ter¬ pene is a monoterpene, such as myrcene or ocimene. In particular, the myrcene starting material for the method according to the first aspect is selected from -myrcene and β-myrcene, most preferably, the myrcene is β-myrcene.
Monoterpenes are dimers of isoprenoid precursors, and myrcene is one of the most important ones because it is a relevant precursor to many terpenes. Myrcene is a monoterpene with a highly active diene structure. It is used in a variety of industrial processes. For example, the technical syntheses of flavors such as menthol, geraniol, nerol, and linalool typically start from myrcene. Moreover, myrcene has been used in organic chemistry for a long time, yielding products for different applications: polymers, pharmaceuticals, insect repellents, flavors and fragrances, vit¬ amins, and biodegradable surfactants. Also, myrcene is a rela¬ tively inexpensive and environmentally friendly starting mate¬ rial .
Examples for the starting conjugated dienes are the following monoterpenes: myrcenes, or 3, 7-dimethyl-l, 3, 7-octatriene ((E)- -ocimene) , (Z) -3, 7-dimethyl-l, 3, 6-octatriene ( (Z) -β-ocimene) , (E) -3, 7 -dimethyl- 1, 3, 6-octatriene ( (E) -β-ocimene) , or 2,6-dime- thyl-2 , 4 , 6-octatriene (allo-ocimene) .
Alternatively, 4, 8-dimethyl-l, 3, 7-nonatriene is used as a start¬ ing conjugated diene.
The chlorination of myrcene may thus proceed as follows:
Figure imgf000014_0001
The myrcene chloride produced is most preferably 3-chloro- - myrcene having the following formula (II)
Figure imgf000014_0002
The reaction is preferably performed in a solvent selected from ethyl acetate, cyclohexane or acetone, or a mixture thereof. The best result due to the best solubility of TCCA was obtained in acetone. Consequently, the most preferred solvent to be used is acetone .
Using the chlorinating agents listed above, any additional un- saturation (e.g. one or more double bonds), as present in the starting conjugated dienes to be functionalized, is retained, i.e. the chlorinating agents result in substitution of a hydrogen atom with a chlorine atom, rather than addition of hydrochloric acid and loss of the additional unsaturation . The chlorinating agent is preferably selected from trichloroisocyanuric acid, di- chloroisocyanuric acid, and mixtures thereof. Most preferably, the chlorinating agent is trichloroisocyanuric acid.
The conjugated diene chloride is an intermediate. It is prefer¬ ably used in a method which produces the functionalized conju¬ gated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000015_0001
(Ilia) (Illb) (IIIc) wherein
R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
Figure imgf000015_0002
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms ,
- R1 is selected from
i) a single bond, one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
- R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms.
The method in one embodiment comprises reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
Figure imgf000016_0001
(Ha) (lib) (He) , with a compound of formula (IV)
Figure imgf000016_0002
)3 (IV) , wherein Y is selected from chlorine, bromine, and iodine atoms.
The Grignard conditions preferably comprise reacting in the presence of magnesium metal, in an ether solvent (such as diethyl ether, or tetrahydrofurane, THF), with a reaction initiator. Preferred reaction initiators are elemental iodine, diisobutyl- aluminium hydride (DIBAH), or 1 , 2-dibromoethane .
In this method, the compound of formula (Ila), (lib), or (lie) can in one embodiment be reacted with magnesium metal first, to prepare the corresponding magnesium Grignard compound, which is in a subsequent step reacted with the compound of formula (IV) .
In an alternative embodiment of the method, the magnesium Gri¬ gnard compound of the compound of formula (Ila), (lib), or (lie) is generated in situ and reacted with the compound of formula (IV) .
The invention consequently in one embodiment relates to the in situ Grignard reaction of chloromyrcene with 1- [ {N, N-bis ( trime- thylsilylamino) } (dimethylsilyl ) ] -2- { chlorodimethylsilyl } - ethane, as follows:
Figure imgf000017_0001
In a further embodiment, the method for the preparation of a functionalized conjugated diene selected from the group of com¬ pounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000018_0001
Sf Si(R5)3
(Ilia) (Illb) (iiic; wherein
R is a linear or branched, saturated or unsaturated hydro¬ carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
Figure imgf000018_0002
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms ,
- R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8, - R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, comprises
A) reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
Figure imgf000019_0001
with a compound of formula (V)
Figure imgf000019_0002
wherein Y1 and Y2 are independently selected from chlorine, bromine, and iodine atoms, and preferably Y1 and Y2 are each chlorine atoms, to result in a compound of formula (IXa), (IXb), (IXc)
Figure imgf000020_0001
(IXa) (IXb) (IXc)
and
B) reacting the compound of formula (IXa), (IXb), (IXc) with a bissilylamide of formula (X)
M
4 /N\ 5
(R )3Si ^Si(R )3
(X) , wherein M is an alkali metal selected from lithium, sodium and potassium, and M is preferably sodium.
The invention also relates to functionalized conjugated dienes selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000020_0002
(Ilia) (Illb) (IIIc) wherein R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la), (lb), (Ic)
Figure imgf000021_0001
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms ,
- R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
- R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms.
In a preferred embodiment of the invention, R1 is ( a) -(CH2)m-, wherein m represents an integer from 1 to 12; or
b) - ( (CH2) mY (CH2) n) o ~ , wherein m and n independently represent an integer from 0 to 12, o is an integer from 1 to 12, and Y is independently one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8.
More preferably, R1 of the functionalized conjugated diene is (iii)b) - (SiR7R8CH2CH2) - .
Moreover, it is preferred according to the invention that R2, R3, R6, R7, and R8 are the same or different and represent C¾ or C6H5, preferably R2, R3, R6, R7, and R8 all represent CH3.
It is in particular preferred that R4 and R5 all represent C¾ .
Regarding the functionalized conjugated diene, the starting con¬ jugated diene selected from the group of compounds of formula
(la), (lb), (Ic) is selected from terpenes and 4 , 8-dimethyl- 1, 3, 7-nonatriene . Preferably the terpene is selected from myr- cene and ocimene, in particular, the terpene is myrcene selected from -myrcene and β-myrcene. Here, it must be noted that the initial chlorination reaction, and the subsequent functionali- zation reaction to give the functionalized conjugated dienes selected from the group of compounds of formula (Ilia), (Illb),
(IIIc), typically proceed in SN2 fashion, and isomerization of the isolated double bond as may be present in the starting con¬ jugated diene of formula (la), (lb), (Ic) may occur. It is for this reason that, even when starting with the method according to the first aspect from specifically β-myrcene or a-myrcene, the resultant functionalized conjugated diene may be a mixture of isomers.
Preferred functionalized conjugated dienes according to the third aspect of the invention are myrcene derivatives of formula (VI), (VII), or (VIII)
Figure imgf000023_0001
Most preferably, the myrcene derivative according to the third aspect of the invention is of formula (Via) , (Vila) , or (Villa)
Figure imgf000024_0001
(Via) (Vila) (Villa)
The following paragraphs relate to preferred embodiments
1. A method for the preparation of a conjugated diene chloride comprising chlorinating a starting conjugated diene selected from the group of compounds of formula (la), (lb), (Ic)
Figure imgf000025_0001
(la) (lb) (Ic) , wherein R is a linear or branched, saturated or unsaturated hydrocarbylene group, and the starting conjugated diene of formula (la), (lb), (Ic) has at least 10 carbon atoms, with a chlorinating agent comprising trichloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of di- chloroisocyanuric acid, or a mixture thereof. The method of paragraph 1, wherein the starting conjugated diene of formula (la), (lb), or (Ic) further contains one or more additional double bonds, preferably wherein the starting conjugated diene contains one additional double bond, more preferably wherein the starting conjugated diene is a terpene or is 4, 8-dimethyl-l, 3, 7-nonatriene . The method of paragraph 2, wherein the terpene is selected from monoterpenes , sesquiterpenes, and diterpenes, preferably wherein the terpene is a monoterpene, more preferably wherein the monoterpene is selected from myr- cene and ocimene, in particular wherein the myrcene is selected from -myrcene and β-myrcene. The method of paragraph 3, wherein the myrcene is β-myrcene. The method of paragraph 4, wherein the myrcene chloride pro¬ duced is 3-chloro-a-myrcene having the following formula (II)
Figure imgf000026_0001
The method of any of the preceding paragraphs, wherein the chlorinating agent is selected from trichloroisocyanuric acid, dichloroisocyanuric acid, and mixtures thereof, preferably wherein the chlorinating agent is trichloroisocy¬ anuric acid.
The method of any of the preceding paragraphs, wherein the reaction is performed in a solvent selected from ethyl ace¬ tate, cyclohexane or acetone, or a mixture thereof, preferably wherein the solvent is acetone. A method for the preparation of a functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000027_0001
(Ilia) (Illb) (IIIc) wherein
R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
Figure imgf000027_0002
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms ,
- R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
- R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comprising reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
Figure imgf000028_0001
(Ha) (lib) (He) , with a compound of formula (IV)
Figure imgf000028_0002
wherein Y is selected from chlorine, bromine, and iodine at¬ oms . A method for the preparation of a functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000029_0001
(Ilia) (Illb) (Hie) wherein
R is a linear or branched, saturated or unsaturated hydro¬ carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
Figure imgf000029_0002
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms ,
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comprising
A) reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
Figure imgf000030_0001
with a compound of formula (V)
Figure imgf000030_0002
wherein Y1 and Y2 are independently selected from chlorine, bromine, and iodine atoms, and preferably Y1 and Y2 are each chlorine atoms, to result in a compound of formula (IXa), (IXb), (IXc)
Figure imgf000031_0001
(IXa) (IXb) (IXc) and
B) reacting the compound of formula (IXa), (IXb), (IXc) with a bissilylamide of formula (X)
M
4 /N\ 5
(R )3Si ^Si(R )3
(X) , wherein M is an alkali metal selected from lithium, sodium and potassium, and M is preferably sodium.
A functionalized conjugated diene selected from the group compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000031_0002
(Ilia) (Illb) (IIIc) wherein R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
Figure imgf000032_0001
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms ,
- R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
- R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms.
11. The functionalized conjugated diene of paragraph 10, wherein R1 is (iii) a) -(CH2)m-, wherein m represents an integer from 1 to 12; or
b) - ( (CH2) mY (CH2) n) o ~ , wherein m and n independently represent an integer from 0 to 12, o is an integer from 1 to 12, and Y is independently one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8. The functionalized conjugated diene of paragraph 11, wherein R1 is (iii)b) - (SiR7R8CH2CH2) - . The functionalized conjugated diene of any of paragraphs 10 to 12, wherein R2, R3, R6, R7, and R8 are the same or different and represent CH3 or Celi5, preferably wherein R2, R3, R6, R7, and R8 all represent C¾ . The functionalized conjugated diene of any of paragraphs 10 to 13, wherein R4 and R5 all represent C¾ . The functionalized conjugated diene of any of paragraphs 10 to 14, wherein the starting conjugated diene of formula (la), (lb), (Ic) is selected from terpenes and 4, 8-dimethyl-l, 3, 7- nonatriene, preferably wherein the terpene is selected from myrcene and ocimene, more preferably wherein the terpene is myrcene selected from -myrcene and β-myrcene. The functionalized conjugated diene of paragraph 15, which is a myrcene derivative of formula (VI), (VII), or (VIII)
Figure imgf000034_0001
)3 (VI) ,
Figure imgf000034_0002
Figure imgf000034_0003
preferably wherein the myrcene derivative is of formula (Via) , (Vila), or (Villa)
Figure imgf000035_0001
(Via ) (Vi l a ) (Vi l la )
The advantages of the present invention become more apparent from the following examples. Unless indicated otherwise, all percentages are given by weight.
Examples
1. Chlorination of myrcene
Reaction procedure: 100 g (0.734 mol) of beta-myrcene and 100 ml of acetone were stirred together. Next, a solution of 96.6 g (0.416 mol) of TCCA in 470 ml of acetone was added dropwise, keeping the temperature below 15°C. After 3 h, a sample was subjected to GC-FID analysis which indicated that the product still contained more than 25 % of unreacted myrcene . Therefore, stirring of the reaction mixture was continued overnight. After completion of the reaction, the obtained mixture was filtered through celite and activated carbon. Then, the solvent was evap¬ orated off, yielding a milky yellow liquid (155.5 g, more than 100% yield, with the product still containing cyanuric acid) . The crude product was distilled under reduced pressure, yielding 50.1 g of yellow liquid (40% yield) . GC-FID chromatographic analysis indicated that the product is a mixture of 3 isomers.
Figure imgf000036_0001
170.679 g/mol
GC-MS :
170.40 (17); 135.44 (22.0); 119.41 (60.0); 93.40 (22.0); 91.38 (51); 79.41 (100); 77.39 (27.0); 65.38 (20); 41.41 (31.0) ; MR:
¾ NMR (600 MHz, CDC13, 300 K) δ (ppm) = 6.40-6.35 (m, 1H, -CH=) , 5.26-5.23 (m, 1H, =CH2) , 5.10-5.08 (m, 1H, =CH2) , 5.06 (m, 1H, =CH2), 5.04 (m, 2H, =CH2) , 4.90 (m, 1H, =CH2) , 4.40 (m, 1H, -CH-), 2.40-2.20 (m, 2H, -CH2-), 2.03 (m, 2H, -CH2-) , 1.83 (m, 3H, -CH3) .
13C NMR (150 MHz, CDC13, 300 K) δ (ppm) = 145.0; 144.4, 138.5; 116.5; 114.3; 113.7; 66.50; 35.20; 28.7; 17.3. 2. In situ Grignard reaction of chloromyrcene
Functionalization of chloromyrcene was performed with 1-[{N,N- bis (trimethylsilylamino) } (dimethylsilyl) ] -2- { chlorodimethylsi- lyljethane. The reaction procedure followed the method of func¬ tionalization as described in WO2016/162473A; and in WO2018/065486A (claiming priority from EP16461559.3) and WO2018/065494A (claiming priority from EP16461560.1) . WO2016/162473A, W02018 / 065486A and WO2018/065494A are incorporated herein by reference. Excellent conversion and yield were obtained .
Chloromyrcene as obtained according to Example 1 was positively tested in the Grignard reaction. GC-FID chromatogram showed myr- cene and its isomers, two unknown impurities and the function- alized conjugated diene monomer of the invention (three iso¬ mers) .
Three main isomers:
Figure imgf000037_0001
-cis β-trans
Mw=439.97 g/mol GC-MS :
439.54 (5.0), 304.46 (7.0), 278.49 (10), 218.44 (100), 202.41 (20), 188.41 (8.0), 151.44 (6.0), 130.38 (12), 73.40 (31) , 59.37 (16) , 45.39 (2) .
NMR :
■"■H MR : data of spectrum corresponding to mixture of isomers, (600 MHz, CDC13, 300 K) δ (ppm) = 6.41-6.29 (m, 1H, -CH=) , 5.27-5.24 (m, 1H, =CH2) , 5.07-5.05 (m, 1H, =CH2) , 5.04-4.99 (broad multiple, 3H, =CH2) , 4.63 (m, 1H, =CH2) , 4.57 (m, 1H, =CH2) , 2.25-2.05 (broad multiple, 4H, -CH2-) , 1.73-1.64 (m, 2H, -CH2-), 1.70 (s, 3H, -CH3) , 1.64-1.59 (m, 2H, -CH2-), 1.62-1.61 (m, 1H, -CH-), 1.62 (s, 3H, -CH3) , 1.53 (s, 3H, -CH3), 1.50 (s, 2H, -Si-CH2) , 0.70-0.44 (m, 4H, Si-CH2-CH2-Si) , 0.20 (m, 18H, -Si- (CH3) 6) , 0.18 (m, 6H, -Si- (CH3)6), 0.02-0.01 (m, 6H, -Si-(CH3)2).
13C NMR : data of spectrum corresponding to mixture of isomers (150 MHz, CDCI3, 300 K) δ (ppm) = 146.76, 146.37, 146.35, 139.15, 133.50, 133.20, 122.19, 121.83, 115.89, 115.73, 115.71, 113.28, 113.13, 113.10, 108.97, 36.87, 31.91, 31.65, 28.11, 27.56, 27.35, 27.08, 26.42, 23.82, 21.65, 18.89, 12.76, 11.91, 11.81, 8.62, 7.98, 5.73, 3.24, 1.11, 2.86, 2.32.
3. Initial Grignard reaction of chloromyrcene with dichloro- dimethylsilane, to give a chlorosilane derivative of myr- cene, followed by reaction with sodium bissilylamide
1 step:
Figure imgf000038_0001
2Νυ step
Figure imgf000039_0001
Experimental procedure:
A 500 ml three-necked round-bottom flask was equipped with a magnetic stir bar, an addition funnel, and a reflux condenser under N2. Mg turnings (4 g, 0.16 mol) were added, followed by anhydrous THF (293 ml), then followed by DIBAH (0.5 ml, 2%mol of Mg) . The activation of Mg was confirmed by the evolution of gas. Dichlorodimethylsilane (15 g, 0.16 mol) was added to the reaction mixture. After stirring for 5 min, chloromyrcene was added with constant rate over a 10-hour time period. Upon completion of the addition, the solution was stirred for another 1 h. The reaction mixture was slowly added to a round-bottom flask containing a 20% solution of bis (trimethylsilyl) amine in THF (or toluene). The resultant mixture was stirred for 2 h. After completion of the reaction, solvent was evaporated, and the obtained solid was filtered, yielding a yellow oil.

Claims

Claims
1. A functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000040_0001
(Ilia) (Illb) (IIIc) wherein
R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the group of compounds of formula (la Ic)
Figure imgf000040_0002
from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms, and the starting conjugated diene of formula (la), (lb), (Ic) is selected from terpenes and 4, 8-dimethyl-l, 3, 7- nonatriene,
- R1 is selected from
i) a single bond, ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
- R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms.
2. The functionalized conjugated diene of claim 1, wherein R1 is (iii) a) -(CH2)m-, wherein m represents an integer from 1 to 12; or
b) - ( (CH2) mY (CH2) n) o ~ , wherein m and n independently represent an integer from 0 to 12, o is an integer from 1 to 12, and Y is independently one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8.
3. The functionalized conjugated diene of claim 2, wherein R1 is (iii)b) - (SiR7R8CH2CH2) - . The functionalized conjugated diene of any of claims 1 to 3, wherein R2, R3, R6, R7, and R8 are the same or different and represent CH3 or Celi5, preferably wherein R2, R3, R6, R7, and R8 all represent CH3.
The functionalized conjugated diene of any of claims 1 to 4, wherein R4 and R5 all represent C¾ .
The functionalized conjugated diene of any of claims 1 to 5, wherein the terpene is selected from monoterpenes , sesquiter¬ penes, and diterpenes, preferably wherein the monoterpene is selected from myrcene and ocimene, more preferably wherein the myrcene is selected from -myrcene and β-myrcene, in particular wherein the myrcene is β-myrcene.
The functionalized conjugated diene of claim 6, which is a myrcene derivative of formula (VI), (VII), or (VIII)
Figure imgf000042_0001
(VI) ,
Figure imgf000043_0001
Figure imgf000043_0002
preferably wherein the myrcene derivative is of formula (Via) , (Vila) , or (Villa)
Figure imgf000044_0001
(Via) (Vila) (Villa)
A method for the preparation of a functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000044_0002
(Ilia) (Illb) (IIIc) wherein
- R is a linear or branched, saturated or unsaturated hydro- carbylene group, and the starting conjugated diene selected from the gro Ic)
Figure imgf000045_0001
(la) (lb) (Ic) , from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms, and the starting conjugated diene of formula (la), (lb), (Ic) is selected from terpenes and 4, 8-dimethyl-l, 3, 7- nonatriene,
- R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
- R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comprising reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
Figure imgf000046_0001
Ha li with a compound of formula (IV)
Figure imgf000046_0002
wherein Y is selected from chlorine, bromine, and iodine at¬ oms .
9. A method for the preparation of a functionalized conjugated diene selected from the group of compounds of formula (Ilia), (Illb), (IIIc)
Figure imgf000046_0003
(Ilia) (Illb) (IIIc) wherein
- R is a linear or branched, saturated or unsaturated hydro¬ carbylene group, and the starting conjugated diene selected from the gro Ic)
Figure imgf000047_0001
(la) (lb) (Ic) , from which the functionalized conjugated diene of formula (Ilia), (Illb), (IIIc) is derived, has at least 10 carbon atoms, and the starting conjugated diene of formula (la), (lb), (Ic) is selected from terpenes and 4, 8-dimethyl-l, 3, 7- nonatriene,
- R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) a hydrocarbylene group which may have one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8,
- R2, R3, R6, R7, R8 can be the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms; and
- R4 and R5 can be the same or different, and each R4 and R5 independently represents an alkyl group containing from 1 to - Al ¬ io carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms, the method comprising
A) reacting, under Grignard conditions, a conjugated diene chloride selected from the group of compounds of formula (Ila), (lib), (lie)
Figure imgf000048_0001
with a compound of formula (V)
Figure imgf000048_0002
wherein Y1 and Y2 are independently selected from chlorine, bromine, and iodine atoms, and preferably Y1 and Y2 are each chlorine atoms, to result in a compound of formula (IXa),
Figure imgf000048_0003
(IXb) (IXc)
and reacting the compound of formula (IXa), (IXb), (IXc) with a bissilylamide of formula (X)
M+
4 5
(R )3Si ^Si(R )3
(X) , wherein M is an alkali metal selected from lithium, sodium and potassium, and M is preferably sodium.
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