CN104876972B - Miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal and synthetic method thereof and the application in preparing alpha, beta-unsaturated carbonyl compound - Google Patents
Miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal and synthetic method thereof and the application in preparing alpha, beta-unsaturated carbonyl compound Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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Abstract
The invention discloses a kind of miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal and synthetic method thereof and the application in preparation α, β beta-unsaturated carbonyl compounds.The structural formula of this complex crystal is
Description
Technical field
The present invention relates to a kind of miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal, and it is preparing α, β-unsaturation as catalyst
Application in carbonyl compound.
Background technology
Cyclopentadienyl titanium complex is stable to air and water, shows high activity and gain great popularity in organic catalysis.But
The development of cyclopentadienyl titanium complex is but confined to identical part, such as cyclopentadienyl titanium dichloride and can be only formed single bigcatkin willow with salicylic acid
Acid cyclopentadienyl titanium chelate and salicyl salicylate (salsalate) cyclopentadienyl titanium complex (Ya Wu, Weiqiang Zhang, Ziwei Gao.Chem.Eur.
J.2014,20,8530-8535), cyclopentadienyl titanium dichloride and benzoic acid can be only formed double benzoic acid cyclopentadienyl titanium complex (Dang Y,
Dommisse R, Esmans E.Journal of Organometallic Chemistry.1990,381 (3), 333-48.),
The acid-base value of reaction can not be finely adjusted in catalytic process by these coordination compounds, thus limit it and develop further
And application.
Alpha, beta-unsaturated carbonyl compound can be used for the intermediate of agricultural chemicals, medicine and spice, liquid crystal polymer
Unit etc., Aldol reaction always builds α, the most basic most important method of beta-unsaturated carbonyl compound.This is anti-
Answer Atom economy high, simple to operate, it is to prepare α, the first-selected approach of beta-unsaturated carbonyl compound.A lotAcid or Lewis acid catalyst are all used for being catalyzed prepares this compounds, and Lewis acid catalyst is the most anti-
Answering mild condition, productivity is higher, but, owing to ketone, the water of aldehyde direct polycondensation generation equivalent of unmodified make
Catalyst activity reduces, and prepares α, and it is that raw material is carried out that the substrate of beta-unsaturated carbonyl compound generally chooses the ketone of modification,
Its raw material preparation complexity, these all make the Aldol reaction of Lewis acid catalysis Atom economy have huge choosing
War.
Summary of the invention
The technical problem to be solved is the luxuriant titanium complex of the identical ligands broken traditions, it is provided that a kind of
Stable to air and water, prepare cheaper starting materials be easy to get, the simple miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of synthesis step, with
And this complex crystal is as catalyst, prepares α, in beta-unsaturated carbonyl compound at catalysis ketone, aldehyde condensation reaction
Application.
Solve above-mentioned technical problem and be the technical scheme is that the structural formula of described miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal
As follows:
In formula, R represents H or F；When R represents H, described miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal belongs to monoclinic system,
P21/ c space group, cell parameter a isB isC isV
Forα is 90 °, and β is 96.290 (5) °, and γ is 90 °, Z=4；When R represents F, described miscellaneous
Bisgallic acid cyclopentadienyl titanium complex crystal belongs to monoclinic system, P21/ c space group, cell parameter a isb
ForC isV isα is 90 °, and β is 107.375 (6) °,
γ is 90 °, Z=4.
The synthetic method of above-mentioned miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal is: by complete with benzoic acid for salicylic acid cyclopentadienyl titanium chelate
Being dissolved in organic solvent, 30～50 DEG C are stirred 1～3 hour, and wherein salicylic acid cyclopentadienyl titanium chelate is with benzoic
Mol ratio is 1:1～1.3, after rotary evaporation solvent evaporated, is the mixed of 1:3 by dichloromethane and normal hexane volume ratio
Closing liquid recrystallization, obtain miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal, synthesis equation is as follows:
Above-mentioned organic solvent is any one in chloroform, acetonitrile, toluene, as long as the addition of organic solvent is protected
Card all substances can be dissolved.Salicylic acid cyclopentadienyl titanium chelate according to literature method (Gao Ziwei, chemistry journal,
2000, volume 58, the 4th phase, 481～485.) synthesis, concrete synthetic method is: by 2.0mmol 5-sulphur
Base salicylic acid is dissolved in 10mL water, is subsequently adding 2.0mmol cyclopentadienyl titanium dichloride, then by molten for 2.2mmol salicylic acid
In 40mL chloroform, then by this two-phase mixtures, after reacting half an hour, separate organic facies, then with saturated
Sodium bicarbonate solution washs 3 times, and anhydrous magnesium sulfate is dried, and filters, evaporated under reduced pressure solvent, is used by the solid of gained
Dichloromethane-normal hexane recrystallization, i.e. obtains salicylic acid cyclopentadienyl titanium chelate.
The present invention miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal prepares alpha, beta-unsaturated carbonyl compound at catalysis Aldol condensation reaction
In purposes, method particularly includes: aldehyde is mixed homogeneously for 1:1.5～2 in molar ratio with ketone, add aldehyde mole
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of 3%～5%, 70～80 DEG C are reacted 0.5～3 hour, obtain α, β-unsaturation carbonyl
Based compound.
Above-mentioned aldehyde isRepresentative H, CH that in formula, X, Y, Z are the most independent3O、CH3、F、
Cl、Br、NO2In any one；Described ketone is Ketohexamethylene.
The luxuriant titanium complex of the identical ligands that the present invention breaks traditions, it is provided that a kind of novel miscellaneous bisgallic acid cyclopentadienyl titanium complex
Crystal, this complex crystal is inexpensive, nontoxic, stable to air and water, and synthetic method is raw materials used cheap and easy to get,
Synthesis step is simple and easy to do, and product post processing is easy, and productivity is high, and prepared by gram level that can realize complex crystal.
The acid-base value of course of reaction can be finely adjusted by the present invention miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal so that it is at Aldol
Condensation reaction shows excellent catalysis activity, can be used for being catalyzed condensation as miscellaneous bisgallic acid synergistic catalyst
Reaction preparation α, beta-unsaturated carbonyl compound, under condition of no solvent, it is catalyzed the ketone of unmodified, aldehyde direct polycondensation
Obtaining the highest productivity in the reaction short time, catalysis activity is high, need not add solvent, simple to operate, atom economy
Property high, the α prepared, beta-unsaturated carbonyl compound is at the intermediate of agricultural chemicals, medicine and spice and liquid
Crystalline polymer unit has the biggest application potential.
Accompanying drawing explanation
Fig. 1 is the x-ray crystal structure figure of the miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of embodiment 1 synthesis.
Fig. 2 is the x-ray crystal structure figure of the miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of the 2-in-1 one-tenth of embodiment.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in more detail, but invention which is intended to be protected is not limited to this
A little embodiments.
Embodiment 1
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal that composite structure formula is following
0.314g (1.0mmol) salicylic acid cyclopentadienyl titanium chelate and 0.122g (1.0mmol) benzoic acid are dissolved in 30mL
In chloroform, 40 DEG C are stirred 2 hours, after rotary evaporation solvent evaporated, are 1:3 by dichloromethane and normal hexane volume ratio
Mixed liquor recrystallization, obtain orange-yellow miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal 0.3925g, its productivity is 90%,
X-ray crystal structure figure is as it is shown in figure 1, it belongs to monoclinic system, P21/ c space group, cell parameter a isB isC isV isα is 90 °, β
Being 96.290 (5) °, γ is 90 °, Z=4, Ti1-O1=1.907 (3), Ti1-O3=1.971 (3), O1-C7=1.209 (5),
O2-C7=1.197 (5), O3-C8=1.282 (6), O4-C8=1.236 (6), O5-C14=1.293 (12),
O1-Ti1-O3=91.69 (15), O2-C7-O1=124.0 (5), C7-O1-Ti1=154.9 (4), O4-C8-O3=123.0 (5),
C8-O3-Ti1=139.4 (3), O1-C7-C1=113.7 (4), O2-C7-C1=124.0 (5), O3-C8-C9=116.3 (4),
O4-C8-C9=120.7 (5).
Embodiment 2
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal that composite structure formula is following
By molten to 0.314g (1.0mmol) salicylic acid cyclopentadienyl titanium chelate and 0.140g (1.0mmol) parafluorobenzoic acid
In 30mL chloroform, 40 DEG C are stirred 2 hours, after rotary evaporation solvent evaporated, with dichloromethane and normal hexane body
The long-pending ratio mixed liquor recrystallization for 1:3, obtains orange-yellow miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal 0.4180g, and it produces
Rate is 92%, and x-ray crystal structure figure is as in figure 2 it is shown, it belongs to monoclinic system, P21/ c space group, structure cell
Parameter a isB isC isV is
α is 90 °, and β is 107.375 (6) °, and γ is 90 °, Z=4, Ti1-O1=1.923 (4), Ti1-O3=1.933 (4),
O1-C11=1.304 (7), O2-C11=1.212 (7), O3-C18=1.282 (7), O4-C8=1.201 (8),
O5-C20=1.286 (9), O1-Ti1-O3=90.5 (2), O1-Ti1-C3=101.5 (2), O3-Ti1-C3=136.9 (2),
O (1)-Ti (1)-C (8)=135.3 (2), O2-C11-O1=124.4 (5), O4-C18-O3=123.2 (7),
O4-C18-C19=121.5 (5), O3-C18-C19=115.3 (6).
Embodiment 3
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of embodiment 1 synthesis is at catalysis benzaldehyde and Ketohexamethylene condensation reaction preparation knot
Structure formula following 2, the purposes in double (phenylmethylene) Ketohexamethylene of 6-, concrete grammar is as follows:
By 101 μ L (1.0mmol) benzaldehydes, 156 μ L (1.5.0mmol) Ketohexamethylene, 21.8mg (0.05mmol)
Miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal is placed in reaction bulb, and 80 DEG C are reacted 2.5 hours, stopped reaction, column chromatography for separation,
Obtaining yellow solid 2, double (phenylmethylene) Ketohexamethylene of 6-, its productivity is 95%.Products therefrom Bruker
Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer characterizes, and characterizes data as follows:1H NMR(400
MHz, CDCl3) δ (ppm): 7.84 (s, 2H), 7.48 (d, J=7.3Hz, 4H), 7.41 (dd,
J=8.1,6.6Hz, 4H), 7.34 (t, J=7.2Hz, 2H), 2.97-2.90 (m, 4H), 1.83-1.75
(m, 2H:13C NMR (101MHz, CDCl3) δ (ppm): 190.37,136.96,136.22,136.00,
130.41,128.62,128.42,28.49,23.04.
Embodiment 4
In embodiment 3, the miscellaneous bisgallic acid cyclopentadienyl titanium of the miscellaneous bisgallic acid cyclopentadienyl titanium complex 2-in-1 one-tenth of crystal embodiment used is joined
Solvate crystal is replaced, and other steps are same as in Example 3, obtain yellow solid 2, double (phenylmethylene) ring of 6-
Hexanone, its productivity is 96%.
Comparative example 1
In embodiment 3, miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal salicyl salicylate (salsalate) cyclopentadienyl titanium complex used is replaced, its
His step is same as in Example 3, obtains yellow solid 2, and double (phenylmethylene) Ketohexamethylene of 6-, its productivity is 83%.
Comparative example 2
In embodiment 3, miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal used is replaced with double benzoic acid cyclopentadienyl titanium complexes, its
His step is same as in Example 3, obtains yellow solid 2, and double (phenylmethylene) Ketohexamethylene of 6-, its productivity is 79%.
Embodiment 5
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of embodiment 1 synthesis is anti-at catalysis P-methoxybenzal-dehyde and Ketohexamethylene condensation
Should prepare that structural formula is following 2, the purposes in double [(4-methoxyphenyl) methylene] Ketohexamethylene of 6-, concrete grammar is such as
Under:
In embodiment 3, benzaldehyde used is replaced with equimolar P-methoxybenzal-dehyde, 80 DEG C of reactions 1.5
Hour, other steps are same as in Example 3, are prepared as yellow solid 2, and 6-is double [(4-methoxyphenyl) methylene]
Ketohexamethylene, its productivity is 97%, characterizes data and is:1H NMR (400MHz, CDCl3) δ (ppm):
7.76 (s, 2H), 7.45 (d, J=8.6Hz, 4H), 6.93 (d, J=8.7Hz, 4H), 3.84 (s,
6H), 2.96-2.87 (m, 4H), 1.80 (dt, J=12.1,6.2Hz, 2H)；13C NMR (101MHz,
CDCl3) δ (ppm): 189.23,158.88,135.50,133.32,131.22,127.73,112.87,54.30,
27.51,22.02.
Embodiment 6
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of embodiment 1 synthesis is in catalysis 4-chloro-benzaldehyde and Ketohexamethylene condensation reaction system
Standby structural formula following 2, the purposes in double (the 4-chlorine benzal) Ketohexamethylene of 6-, concrete grammar is as follows:
In embodiment 3, benzaldehyde used is replaced with equimolar 4-chloro-benzaldehyde, and 80 DEG C are reacted 3 hours, its
His step is same as in Example 3, is prepared as yellow solid 2, and double (the 4-chlorine benzal) Ketohexamethylene of 6-, its productivity is
98%, characterizing data is:1H NMR (400MHz, CDCl3) δ (ppm): 7.73 (s, 1H), 7.41-7.35
(m, 4H), 2.92-2.86 (m, 2H), 1.80 (dt, J=12.4,6.3Hz, 1H)；13C NMR
(101MHz, CDCl3) δ (ppm): 189.88,136.43,135.79,134.63,134.32,131.59,
128.69,28.38,22.82.
Embodiment 7
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of embodiment 1 synthesis is in catalysis 4-Fluorobenzaldehyde and Ketohexamethylene condensation reaction system
Standby structural formula following 2, the purposes in double (the 4-fluorine benzal) Ketohexamethylene of 6-, concrete grammar is as follows:
In embodiment 3, benzaldehyde used is replaced with equimolar 4-Fluorobenzaldehyde, and 80 DEG C are reacted 3 hours,
Other steps are same as in Example 3, are prepared as yellow solid 2, double (the 4-fluorine benzal) Ketohexamethylene of 6-, its productivity
Being 97%, characterizing data is:1H NMR (400MHz, CDCl3) δ (ppm): 7.75 (s, 2H),
7.45 (dd, J=8.5,5.6Hz, 4H), 7.10 (t, J=8.6Hz, 4H), 2.93-2.86 (m, 4H),
1.85-1.76 (m, 2H)；13C NMR (101MHz, CDCl3) δ (ppm): 188.99,160.40,
134.85,131.28,131.20,114.61,114.40,27.32,21.88.
Embodiment 8
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of embodiment 1 synthesis is at catalysis o-bromobenzaldehye and Ketohexamethylene condensation reaction
Prepare that structural formula is following 2, the purposes in double (the 4-bromine benzal) Ketohexamethylene of 6-, concrete grammar is as follows:
In embodiment 3, benzaldehyde used is replaced with equimolar o-bromobenzaldehye, and 80 DEG C are reacted 3 hours,
Other steps are same as in Example 3, are prepared as yellow solid 2, double (the 2-bromine benzal) Ketohexamethylene of 6-, its productivity
Being 91%, characterizing data is:1H NMR (400MHz, CDCl3) δ (ppm): 7.85 (s, 2H),
7.64 (d, J=8.0Hz, 2H), 7.35-7.29 (m, 4H), 7.22-7.17 (m, 2H), 2.78-2.72
(dt, 4H), 1.76 (m, J=6.1Hz, 2H)；13C NMR (101MHz, CDCl3) δ (ppm):
189.64,137.43,136.40,136.29,132.97,130.53,129.71,126.88,125.15,28.29,
23.11。
Embodiment 9
The miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of embodiment 1 synthesis is at catalysis 4-tolyl aldehyde and Ketohexamethylene condensation reaction
Prepare that structural formula is following 2, the purposes in double (4-methylbenzilidene) Ketohexamethylene of 6-, concrete grammar is as follows:
In embodiment 3, benzaldehyde used is replaced with equimolar 4-tolyl aldehyde, and 80 DEG C of reactions 1.5 are little
Time, other steps are same as in Example 3, are prepared as yellow solid 2, double (4-methylbenzilidene) Ketohexamethylene of 6-,
Its productivity is 96%, characterizes data and is:1H NMR (400MHz, CDCl3) δ (ppm): 7.78 (s, 2H),
7.38 (d, J=8.0Hz, 4H), 7.22 (d, J=7.9Hz, 4H), 2.96-2.90 (m, 4H), 2.38
(s, 6H), 1.79 (dt, J=12.3,6.3Hz, 2H)；13C NMR (101MHz, CDCl3) δ (ppm):
190.43,138.81,136.88,135.51,133.23,130.49,129.14,28.54,23.04,21.41.
Claims (7)
1. a miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal, it is characterised in that the structural formula of this coordination compound is as follows:
In formula, R represents H or F.
Miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal the most according to claim 1, it is characterised in that: when R represents H,
Described miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal belongs to monoclinic system, P21/ c space group, cell parameter a is B isC isV isα is 90 °, and β is 96.290 (5) °,
γ is 90 °, Z=4.
Miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal the most according to claim 1, it is characterised in that: when R represents F,
Described miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal belongs to monoclinic system, P21/ c space group, cell parameter a is B isC isV isα is 90 °, and β is 107.375 (6) °,
γ is 90 °, Z=4.
4. the synthetic method of the miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal described in a claim 1, it is characterised in that:
Salicylic acid cyclopentadienyl titanium chelate is dissolved in organic solvent with benzoic acid or parafluorobenzoic acid 1:1 in molar ratio～1.3,
30～50 DEG C are reacted 1～3 hour, are spin-dried for organic solvent, recrystallization, obtain miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal；
Described organic solvent is any one in chloroform, acetonitrile, toluene.
5. the miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal described in claim 1 prepares α, β-insatiable hunger at catalysis Aldol condensation reaction
With the purposes in carbonyl compound.
Miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal the most according to claim 5 catalysis Aldol condensation reaction prepare α, β-
Purposes in beta-unsaturated carbonyl compounds, it is characterised in that: aldehyde is mixed homogeneously for 1:1.5～2 in molar ratio with ketone,
Adding the miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal of aldehyde mole 3%～5%, 70～80 DEG C are reacted 0.5～3 hour, obtain
Alpha, beta-unsaturated carbonyl compound.
Miscellaneous bisgallic acid cyclopentadienyl titanium complex crystal the most according to claim 6 catalysis Aldol condensation reaction prepare α, β-
Purposes in beta-unsaturated carbonyl compounds, it is characterised in that: described aldehyde isX in formula, Y,
Representative H, CH the most independent for Z3O、CH3、F、Cl、Br、NO2In any one；Described ketone is
Ketohexamethylene.
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