CN106565759A - Preparation method and application of 1,4-diboric acid ester-2-butyne - Google Patents
Preparation method and application of 1,4-diboric acid ester-2-butyne Download PDFInfo
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- CN106565759A CN106565759A CN201610937459.3A CN201610937459A CN106565759A CN 106565759 A CN106565759 A CN 106565759A CN 201610937459 A CN201610937459 A CN 201610937459A CN 106565759 A CN106565759 A CN 106565759A
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- butyne
- nitrae
- isosorbide
- diborate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960002415 trichloroethylene Drugs 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- -1 4- tolyl aldehydes Chemical class 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ZIIGSRYPZWDGBT-UHFFFAOYSA-N 610-30-0 Chemical class OC(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O ZIIGSRYPZWDGBT-UHFFFAOYSA-N 0.000 claims description 5
- NVYYDIPNVIISQO-UHFFFAOYSA-N CC(C)(C(C)(C=C)O)O.OB(O)O.I Chemical compound CC(C)(C(C)(C=C)O)O.OB(O)O.I NVYYDIPNVIISQO-UHFFFAOYSA-N 0.000 claims description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 150000005341 2-nitrobenzoic acids Chemical class 0.000 claims description 4
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical class BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006772 olefination reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 claims description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000005698 Diels-Alder reaction Methods 0.000 abstract description 3
- 238000006735 epoxidation reaction Methods 0.000 abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 239000004327 boric acid Substances 0.000 abstract description 2
- 238000001212 derivatisation Methods 0.000 abstract description 2
- 229910052740 iodine Inorganic materials 0.000 abstract description 2
- 239000011630 iodine Substances 0.000 abstract description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 150000003333 secondary alcohols Chemical group 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005937 allylation reaction Methods 0.000 description 2
- 150000001642 boronic acid derivatives Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a preparation method and application of 1,4-diboric acid ester-2-butyne. The preparation method comprises the steps of performing pinacol ester reaction of trichloro ethylene and iodine methylene boric acid by regarding n-butyllithium as alkali, and obtaining a product 1,4-diboric acid ester-2-butyne through separation and purification; performing tandem propargyl/guildline alkenyl reaction on 1,4-diboric acid ester-2-butyne and aromatic aldehyde to prepare a 1,3-butadiene-2,3-di-secondary alcohol compound. The preparation method is simple and convenient to operate; the used reagents are nontoxic, green and environment-friendly; the prepared 1,3-butadiene-2,3-di-secondary alcohol compound can be further subjected to derivatization through Diels-Alder or Shapless epoxidation reaction, and is an important organic synthon.
Description
Technical field
The invention belongs to organic compound synthesis and applied technical field, are related to the preparation of Isosorbide-5-Nitrae-diborate -2-butyne
Method and with application which is two secondary alcohol compounds of Material synthesis 1,3- butadiene -2,3-.
Background technology
The critical nature such as organoboron compound has nontoxic, good stability and reactivity is adjustable, is that a class is important
Organic synthesis reagent [Kennedy, J.W.J.；Hall,D.G.Angew.Chem.,Int.Ed.2003,42,4732-4739；
Denmark,S.E.；Fu,J.Chem.Rev.2003,103,2763；Huo,H.-X.；Duvall,J.R.；Huang,M.-Y.；
Hong,R.Org.Chem.Front.2014,1,303.].Unsaturated double cascade reactions between borate and carbonyl containing compound
Complicated useful product can be built, so as to draw attention.
2013, Morken groups obtained chiral unsaturated vicinal by asymmetric boron glycosylation reaction from 1,3-butadiene
The double borates in position, next allylation reaction generates chiral cyclohexyl Isosorbide-5-Nitrae-glycol twice with Isosorbide-5-Nitrae-dicarbonyl compound Jing again
Class compound (Ferris, G.E.；Hong,K.；Roundtree,I.A.；Morken,J.P.J.Am.Chem.Soc.2013,
135,2501.).At the same time, Roush groups obtain chiral double borates using the hydroboration of connection ene boric acid ester, so
Simple aldehyde reactions different from two kinds respectively again has successfully synthesized chiral 1,5- glycolss product (Chem, M. afterwards；Roush,
W.R.J.Am.Chem.Soc.2013,135,9512.).2015, Szab ó groups were using butadienyl neighbour's diborate and aldehyde
For reaction raw materials, allylation/connection olefination is concatenated, obtains Isosorbide-5-Nitrae-glycol (Zhao, T.S.N.；Zhao,J.；Szab
ó,K.J.Org.Lett.2015,17,2290.).As can be seen here, the synthetic method of the double boronate reagents of Development of Novel and its synthesis
It is of great significance using tool.
The synthesis of Isosorbide-5-Nitrae-diborate -2-butyne yet there are no document report, its be concatenated with two equivalent aldehyde propargyl/
High connection olefination will likely obtain 1,3- butadiene -2,3- di-secondary alcohol products.1,3- butadiene -2- in product structure
Secondary alcohol skeleton is widely present in natural product, can also be derived by Diels-Alder or Shapless epoxidation reactions,
So as to synthesize increasingly complex molecule.
The content of the invention
It is an object of the invention to disclose a kind of preparation method of 1,4- diborates -2-butyne and with which as Material synthesis
The application of two secondary alcohol of 1,3- butadiene -2,3-.The method is easy to operate, and the reaction reagent for being used is nontoxic, environmental protection.This
Bright technical scheme is as follows：
The preparation method of Isosorbide-5-Nitrae-diborate -2-butyne, the method make alkali with n-BuLi, sub- with iodine by trichloro ethylene
Methyl-boric acid pinacol ester reacts, and the separated purification of product obtains Isosorbide-5-Nitrae-diborate -2-butyne, and reaction expression is as follows：
In such scheme, the preparation method of Isosorbide-5-Nitrae-diborate -2-butyne is specific as follows：In -78 DEG C, N2Protective atmosphere
Under, trichloro ethylene is slowly dropped in the diethyl ether solution of n-BuLi, 30 DEG C of stirring reactions 12 is warming up to after being added dropwise to complete little
When, -78 DEG C are then cooled to, iodine methylene pinacol borate is slowly dropped in mixed solution, continued after being added dropwise to complete
Reaction 2h, adds water after solution is warming up to 30 DEG C of reaction 48h finally and is quenched, isolate and purify and obtain final product.
With Isosorbide-5-Nitrae-diborate -2-butyne as Material synthesis 1,3-butadiene -2, the application of bis- secondary alcohol of 3-, the method are concrete
For：Under uniform temperature, olefination is joined with propargyl of the connecting/height of aromatic aldehyde by Isosorbide-5-Nitrae-diborate -2-butyne, is prepared
1,3-butadiene -2 are obtained, bis- secondary alcohol compounds of 3-, its reaction expression are as follows：
In such scheme, the aromatic aldehyde is benzaldehyde, 4- tolyl aldehydes, the one kind in 4- bromobenzaldehydes.
In such scheme, the catalyst for being used is 2- nitrobenzoic acids, pentafluorobenzoic acid, phenyl-phosphonic acid, phosphoric acid hexichol
One kind in ester, 2,4- dinitrobenzoic acids, Cu-lyt., zinc chloride.
In such scheme, the solvent for being used is toluene, the one kind in tetrahydrofuran.
In such scheme, the reaction temperature is 30 DEG C, 50 DEG C or 80 DEG C.
The invention has the advantages that：Easy to operate, the reaction reagent for being used is nontoxic, environmental protection, by this
1,3-butadiene -2 that method is prepared, bis- secondary alcohol compounds of 3-, can further pass through Diels-Alder or
Shapless epoxidation reactions are performed the derivatization.
Specific embodiment
To make those skilled in the art fully understand technical scheme and beneficial effect, below in conjunction with being embodied as
Example is further described.
The preparation method of Isosorbide-5-Nitrae-diborate -2-butyne, its step is：In N2, under the conditions of -78 DEG C, made with n-BuLi
Alkali, the Deca trichloro ethylene in flask；After being added dropwise to complete, mixed solution temperature is risen to into 30 DEG C and is reacted 12 hours, it is then cold again
But to -78 DEG C；Then to mixed solution and dripping iodine methylene pinacol borate, after completion of dropping, continue reaction 2 hours, then
It is warming up to 30 DEG C to react 48 hours；Add water after the completion of reaction and be quenched, isolate and purify and obtain product Isosorbide-5-Nitrae-diborate -2-butyne,
Reaction expression is as follows：
With Isosorbide-5-Nitrae-diborate -2-butyne as Material synthesis 1,3-butadiene -2, the application of bis- secondary alcohol of 3-, its step is：
In N2Under the conditions of atmosphere, 30 DEG C or 50 DEG C or 80 DEG C, by aromatic aldehyde (benzaldehyde, 4- tolyl aldehydes, 4- bromobenzaldehydes), Isosorbide-5-Nitrae-
Diborate -2-butyne, toluene or THF solvents, catalyst (2- nitrobenzoic acids, pentafluorobenzoic acid, phenyl-phosphonic acid, di(2-ethylhexyl)phosphate
Phenyl ester, 2,4- dinitrobenzoic acids, Cu-lyt., zinc chloride) mixing, it is anti-that stirring 48h carries out series connection propargyl/height connection alkenyl
Answer, then Jing column chromatography for separation obtains product 1,3-butadiene -2, bis- secondary alcohols of 3-, its reaction expression are as follows：
Agents useful for same of the present invention is common commercially available, AR.
Embodiment 1
The preparation of 1,4- diborates -2-butyne.
Under nitrogen atmosphere, 45mL THF/Et are added in two mouthfuls of flasks of 250mL2O (volume ratios 1:1) mixed solvent with
And the diethyl ether solution (2.5M, 43.7mmol) of 17.5mL n-BuLis, stir and be cooled to -78 DEG C.By 1.3mL trichloro ethylenes
(14.6mmol) it is dissolved in 10mL absolute ethers, is slowly added dropwise into above-mentioned mixed solution, after being added dropwise to complete, is warming up to 30
DEG C stirring reaction 12 hours, obtains white turbid liquid.Under nitrogen atmosphere, by the anhydrous of iodine methylene pinacol borate (7.8g)
Diethyl ether solution (50mL) is cooled to -78 DEG C, and above-mentioned white turbid liquid syringe is slowly dropped in the solution for having cooled down.Deca
Continue to react 2 hours at -78 DEG C after finishing, be then to slowly warm up to 30 DEG C of reaction 48h.After reaction terminates, 30mL water is added
It is quenched and reacts and point liquid, then with 30mL ethyl acetate aqueous phase extracted twice, merges organic faciess, it is using anhydrous sodium sulfate drying, dense
Reddish brown color cloud liquid is obtained after contracting.Crude on silica gel column chromatographic isolation and purification, obtains weak yellow liquid (Isosorbide-5-Nitrae-diborate -2-
Butine) 2.25g, yield 50%.1H NMR(500MHz,CDCl3)δ1.78(s,4H),1.26(s,24H)。
Embodiment 2
The preparation of two secondary alcohols of 1,3- butadiene -2,3-
Under nitrogen atmosphere, benzaldehyde (10.6mg, 0.1mmol), Isosorbide-5-Nitrae-diborate -2-butyne are added in reaction bulb
(15.3mg, 0.05mmol), 2- nitrobenzoic acids (1.0mg, 10mol%) and dry toluene (0.25mL), stir at 30 DEG C anti-
Column chromatography for separation is directly carried out after answering 48 hours, target product 1,3-butadiene -2, bis- secondary alcohols of 3- are obtained.Yield is
51%, dr=3.8:1.
Embodiment 3-10
Catalyst, solvent and reaction temperature are optimized on the basis of embodiment 2, has equally successfully synthesized 1,3- fourths
Diene -2, bis- secondary alcohols of 3-, actual conditions and experimental result it is as shown in table 1.
Synthesize the synopsis of two secondary alcohols of 1,3- butadiene -2,3- under 1 different condition of table
Embodiment 11
The preparation of two secondary alcohols of 1,3- butadiene -2,3-.
Under nitrogen atmosphere, 4- tolyl aldehydes (12.0mg, 0.1mmol), Isosorbide-5-Nitrae-diborate -2- are added in reaction bulb
Butine (15.3mg, 0.05mmol), 2,4- dinitrobenzoic acids (1.1mg, 10mol%) and dry toluene (0.25mL), 30 DEG C
Lower stirring reaction directly carries out column chromatography for separation after 48 hours, obtain target product 1,3-butadiene -2, bis- secondary alcohols of 3-.
Yield 53%, dr=3.9:1.1H NMR(500MHz,CDCl3)δ7.24-7.05(m,8H),5.37(s,2H),5.25(d,
14.2Hz,2H),5.14(d,7.8Hz,2H),2.34(s,6H)。
Embodiment 12
The preparation of two secondary alcohols of 1,3- butadiene -2,3-.
Under nitrogen atmosphere, 4- bromobenzaldehydes (17.1mg, 0.1mmol), Isosorbide-5-Nitrae-diborate -2- fourths are added in reaction bulb
Alkynes (15.3mg, 0.05mmol), 2,4- dinitrobenzoic acids (1.1mg, 10mol%) and dry toluene (0.25mL), at 30 DEG C
Stirring reaction directly carries out column chromatography for separation after 48 hours, obtain target product 1,3-butadiene -2, bis- secondary alcohols of 3-.Produce
Rate 34%, dr=3.8:1.1H NMR(500MHz,CDCl3)δ7.41(dd,22.2,8.4Hz,4H),7.12(dd,42.0,
7.9Hz,4H),5.33(d,11.8Hz,2H),5.24(d,24.5Hz,2H),5.12(d,25.8Hz,2H)。
Obviously, above example is just for the sake of clearly demonstrating done example, and the not restriction to embodiment.
For person of an ordinary skill in the technical field, many other not similar shapes can also be made on the basis of foregoing invention
The change or change of formula, these changes or change all should fall under the scope of the present invention.
Claims (7)
- The preparation method of 1.1,4- diborates -2-butyne, it is characterised in that the method makees alkali with n-BuLi, by trichlorine Ethylene is reacted with iodine methylene pinacol borate, and the separated purification of product obtains Isosorbide-5-Nitrae-diborate -2-butyne, reaction expression It is as follows：
- 2. the preparation method of Isosorbide-5-Nitrae-diborate -2-butyne as claimed in claim 1, it is characterised in that the method is specifically such as Under：In -78 DEG C, N2Under protective atmosphere, trichloro ethylene is slowly dropped in the diethyl ether solution of n-BuLi, is risen after being added dropwise to complete Temperature is then cooled to -78 DEG C, iodine methylene pinacol borate is slowly dropped to mixing molten to 30 DEG C of stirring reactions 12 hours In liquid, after being added dropwise to complete, continue reaction 2h, add water after solution is warming up to 30 DEG C of reaction 48h finally and be quenched, isolate and purify and obtain final product.
- 3.1,4- diborates -2-butyne is used to synthesize 1,3-butadiene -2, the application of bis- secondary alcohol of 3-, it is characterised in that：Necessarily At a temperature of, olefination is joined with propargyl of the connecting/height of aromatic aldehyde by Isosorbide-5-Nitrae-diborate -2-butyne, is prepared 1,3-butadiene -2, bis- secondary alcohol compounds of 3-, its reaction expression are as follows：
- 4. the application of Isosorbide-5-Nitrae-diborate -2-butyne as claimed in claim 3, it is characterised in that：The aromatic aldehyde is benzene first One kind in aldehyde, 4- tolyl aldehydes, 4- bromobenzaldehydes.
- 5. the application of Isosorbide-5-Nitrae-diborate -2-butyne as claimed in claim 3, it is characterised in that：The catalyst for being used is 2- nitrobenzoic acids, pentafluorobenzoic acid, phenyl-phosphonic acid, diphenyl phosphate, 2,4- dinitrobenzoic acids, Cu-lyt., zinc chloride In one kind.
- 6. the application of Isosorbide-5-Nitrae-diborate -2-butyne as claimed in claim 3, it is characterised in that：The solvent for being used is first One kind in benzene, tetrahydrofuran.
- 7. the application of Isosorbide-5-Nitrae-diborate -2-butyne as claimed in claim 3, it is characterised in that：The reaction temperature is 30 DEG C, 50 DEG C or 80 DEG C.
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| HERBERT C. BROWN ET AL.: "Chiral Synthesis via Organoboranes. 17. Preparation of α-Chiral α"-Alkynyl Ketones of High Enantiomeric Excess from Optically PureOrganyl( 1-alkyny1)borinic Esters", 《J. ORG. CHEM.》 * |
| HERBERT C.BROWN ET AL.: "A Simple, Convenient, General Procedure for the Synthesis of 2-Alkyn-l-yiboronates", 《TETRAHEDRON LETTERS》 * |
| RAMAN SOUNDARARAJAN ET AL.: "General synthesis of 2-alkyn-1-ylboronates in excellent isomeric purity", 《TETRAHEDRON LETTERS》 * |
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