WO2019030059A1 - Diènes conjugués fonctionnalisés par bissilylaminosilyle et procédés pour leur préparation - Google Patents

Diènes conjugués fonctionnalisés par bissilylaminosilyle et procédés pour leur préparation Download PDF

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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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group
formula
conjugated diene
carbon atoms
myrcene
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PCT/EP2018/070768
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English (en)
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Maria SIOLEK
Radoslaw KOZAK
Pawel WEDA
Robert BOGACZ
Tomasz SKROK
Dawid BARTUS
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Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna
Synthos S.A.
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Publication of WO2019030059A1 publication Critical patent/WO2019030059A1/fr

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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

L'invention concerne des diènes conjugués fonctionnalisés par bissilylaminosilyle de formule (IIIa), (IIIb) ou (IIIc) (formule IIIa, b, c) et leurs procédés de préparation. Les diènes conjugués de formule (IIIa), (IIIb) ou (IIIc) sont à base de terpènes ou de 4,8-diméthyl-1, 3, 7-nonatriène en tant que matières premières.
PCT/EP2018/070768 2017-08-08 2018-07-31 Diènes conjugués fonctionnalisés par bissilylaminosilyle et procédés pour leur préparation WO2019030059A1 (fr)

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WO2020152332A1 (fr) 2019-01-24 2020-07-30 Synthos S.A. Diènes conjugués fonctionnalisés par bissilylamino, leur préparation et leur utilisation dans la production de caoutchoucs
US11312843B2 (en) 2017-08-08 2022-04-26 Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna Bissilylaminosilyl-functionalized conjugated dienes and their use in the production of rubbers

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US11312843B2 (en) 2017-08-08 2022-04-26 Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna Bissilylaminosilyl-functionalized conjugated dienes and their use in the production of rubbers
WO2020152332A1 (fr) 2019-01-24 2020-07-30 Synthos S.A. Diènes conjugués fonctionnalisés par bissilylamino, leur préparation et leur utilisation dans la production de caoutchoucs

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