CN104557448B - The method of Fluoroacetylenes is prepared with alkynes and chloro-1,1, the 1-Halothane generation linked reaction of 2,2-bis- - Google Patents
The method of Fluoroacetylenes is prepared with alkynes and chloro-1,1, the 1-Halothane generation linked reaction of 2,2-bis- Download PDFInfo
- Publication number
- CN104557448B CN104557448B CN201410770656.1A CN201410770656A CN104557448B CN 104557448 B CN104557448 B CN 104557448B CN 201410770656 A CN201410770656 A CN 201410770656A CN 104557448 B CN104557448 B CN 104557448B
- Authority
- CN
- China
- Prior art keywords
- alkyl
- alkynes
- chloro
- halothane
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of with alkynes and 2,2-bis-chloro-1,1,1-Halothane generation linked reaction prepares the method for Fluoroacetylenes, specifically in polar organic solvent and when heating, under secondary amine exists, cuprous or the Z of alkynyl replaces alkynes, 2,2-bis-chloro-1,1,1-Halothane and copper powder generation linked reaction obtain Fluoroacetylenes.It can be alkyl that described Z replaces alkynes, thiazolinyl, aryl, contains the aryl to electron substituent group or halogen substiuted, the alkyl etc. containing double bond, hydroxyl, thioether, ether, alkene alkoxyl group, uncle's amino or ester group group.The copper that present method is cheap and diethylamine achieve the linked reaction of alkynes and chloro-1,1, the 1-Halothane of 2,2-bis-in organic polar solvent.Reaction conditions is fairly simple, easy handling, is a kind of potential method solving fluorohaloparaffin and pollute.
Description
Technical field
The present invention relates to the alkynes of a kind of copper participation and the linked reaction of chloro-1,1, the 1-Halothane of 2,2-bis-, specifically a kind of using alkynes as nucleophilic reagent and CF
3cHCl
2there is the method that linked reaction prepares Fluoroacetylenes.
Technical background
Due to the characteristic of fluorine atom stereoeffect and electronic effect, fluorinated organic compound is made to be widely used in medicine, agricultural chemicals, in the fields such as novel material.In these organic fluorocompounds, fluorochloroparaffins micromolecular compound, as the by product produced inevitable in fluorine chemical, is often used as refrigeration agent with the character of its uniqueness, washing composition and whipping agent etc.But scientists finds, fluorochloroparaffins is discharged in air, is excited rear generation chlorine radical, thus have extremely strong destruction to ozonosphere by the solar ultraviolet of short wavelength.Therefore, according to " Montreal Agreement ", fluorochloroparaffins will be completely forbidden use in the year two thousand thirty.But chemically angle is seen, this compounds is inherently containing the Guan Nengtuan such as trifluoromethyl, and can the chemical process that develop new cheapness make it be converted into a kind of fluoro-building block to have great importance.
Organic functional molecular based on the unsaturated compound such as alkynes and alkene synthesis high added value is the focus of modern organic synthesis always.The reaction of application alkynes has been applied to the synthesis of the functional moleculars such as numerous natural products, medicine, agricultural chemicals, luminescent material, fire retardant material, polymkeric substance, organic synthesis intermediate, plays irreplaceable effect in modern organic synthesis.And Fluoroacetylenes is due to the special property of fluorine, widespread use is in all fields: l) fluoro-resin, the fluoropolymers such as viton and functional materials, 2) weedicide, the fluorine-containing agrochemicals such as sterilant and sterilant, 3) Drugs Containing Fluorine, comprise: narcotic, various anticarcinogen, anti-inflammation analgesia medicine, tranquilizer, antiviral etc.The special property of organofluorine compound comes from following four aspects: 1. pseudo-plan effect and blocking effect, the 2. high electronegativity of fluorine atom, 3 is fat-soluble, 4. hydrogen bond.
In recent years, scientists achieved a series of achievement in the chemical conversion of fluorine-containing organic molecule.Such as, CF
3cH
2i, BrCF
2p (O) OR, BrCF
2cH=CH
2, C
4f
9iCF
3the fluorine-containing iodo thing such as I and bromo-derivative have also been successfully applied and the linked reaction of nucleophilic reagent or the Radical Addition with unsaturated compound.Fluorine-containing chloro thing is because its carbon chlorine key is more than carbon iodine key or carbon bromine key inertia, and the report of relevant chemical conversion is few.The laboratory of the present inventor has made some progress in this respect, but reactant is confined to alkene, phenol oxygen, aryl thiophenol.
Alkynyl can carry out multiple conversion as the group that activity is very high, and Ma (Maetal.Angew.Chem.Int.Ed.2012,51,6227.) and Xu (Xuetal.Org.Lett.2013,15,936.) uses the CF with explosion hazard respectively
3cHN
2with the CF of costliness
3cH
2i achieves the linked reaction with alkynes as fluoro-building block, but reaction conditions religion is harsh, and economy is poor.The present inventor's imagination realizes itself and CF using alkynes as nucleophilic reagent
3cHCl
2linked reaction build Fluoroacetylenes, but realizing this reaction has certain challenge: carbon chlorine key very inertia, even if fracture, if produce free radical be easy to protonated; If create negatively charged ion, be easy to β-F eliminative reaction occurs.
Summary of the invention
In order to solve above-mentioned difficulties, the invention provides the alkynes of a kind of copper participation and the linked reaction of chloro-1,1, the 1-Halothane of 2,2-bis-, namely using alkynes as nucleophilic reagent and CF
3cHCl
2there is the method that linked reaction prepares Fluoroacetylenes.
Method of the present invention is as follows: time in polar organic solvent with 55 DEG C ~ 90 DEG C, at two (C
2-C
8alkyl) amine or two (C
2-C
4thiazolinyl) under amine exists, the cuprous or Z of alkynyl replaces alkynes, and chloro-1,1, the 1-Halothane of 2,2-bis-and copper powder generation linked reaction obtain Fluoroacetylenes in 1 ~ 10 hour, adopt the longer reaction times not affect reaction; Cuprous or the Z of described alkynyl replaces alkynes, chloro-1,1, the 1-Halothane of 2,2-bis-, copper powder, two (C
2-C
8alkyl) amine or two (C
2-C
4thiazolinyl) mol ratio of amine is followed successively by: 1:0.5-20:0.5-5:1-5.
In present method, adopt more 2,2-bis-chloro-1,1,1-Halothane or copper powder also on reaction not impact, recommend when alkynyl is cuprous, chloro-1,1, the 1-Halothane of 2,2-bis-, copper powder, two (C
2-C
8alkyl) amine or two (C
2-C
4thiazolinyl) amine generation linked reaction time, mol ratio is followed successively by 1:1-5:0-5:1-5; Z replaces alkynes, chloro-1,1, the 1-Halothane of 2,2-bis-, copper powder, two (C
2-C
8alkyl) amine or two (C
2-C
4thiazolinyl) amine generation linked reaction time, corresponding mol ratio is 1:1-5:0-5:1-5; Preferential mol ratio is 1:1-5:0.5-5:1-5.When Z replaces alkynes, chloro-1,1, the 1-Halothane of 2,2-bis-, copper powder, two (C
2-C
8alkyl) amine or two (C
2-C
4thiazolinyl) amine generation linked reaction time, recommend corresponding mol ratio be followed successively by 1:1-5:0.5-5:1-5.
Above-mentioned Z substituting group can be C
1-C
12alkyl, C
2-C
12thiazolinyl, aryl, containing to the aryl of electron substituent group or halogen substiuted, the C containing double bond, hydroxyl, thioether, ether, alkene alkoxyl group, tertiary amine groups or ester group group
3-C
24alkyl.Described aryl can be phenyl or naphthyl.Described Z is preferably C
2-C
12alkyl, C
2-C
12thiazolinyl, C
4-C
8cycloalkenyl group, C
1-C
12the C that alkoxyl group replaces
2-C
12alkyl, C
2-C
6the C of alkenyl substituted
1-C
12alkyl, phenyl, the phenyl that R replaces, C
1-C
12alkylthio C
2-C
12alkyl, arylthio C
2-C
12alkyl, methoxyphenyl sulfo-C
1-C
6alkyl, N-C
1-C
8alkyl, N-C
1-C
8the tertiary amine C of alkyl
1-C
8alkyl, C
1-C
4alkyl carboxylic acid C
2-C
12alkane fat base or fragrant C
1-C
4alkyl carboxylic acid C
2-C
12alkane fat base etc.Wherein R is halogen, C
1-C
8alkyl, C
1-c
8alkoxyl group.
Two described (C
2-C
8alkyl) amine or two (C
2-C
4thiazolinyl) amine can be diethylamine, diallyl amine, N, N`-dimethyl-ethylenediamine, Tetramethyl Ethylene Diamine etc.
Described organic polar solvent can be methylene dichloride, 1,2-ethylene dichloride, acetonitrile, chloro-1,1, the 1-Halothane equal solvent of 2,2-bis-.
Adopt method of the present invention, above-mentioned product can by following method purifying: organic solvent extraction, filtration, distillation removing excess of solvent or obtain product through column chromatography for separation etc.
Such as, cuprous (the synthesis that alkynyl is cuprous: Theunissenetal.Synthesis2014 of alkynyl has been synthesized by document, 46,1157), under the existence of the diethylamine of two moles and when DCE makees solvent, alkynyl is cuprous with 2,2-bis-chloro-1,1,1-Halothane generation linked reaction, can obtain the product of alkynyl end trifluoroethyl with the yield of 34%.And in reactant, add the copper powder of a mole, reaction yield can be brought up to 60%.
Wherein, DCE is ethylene dichloride.
In view of above result, carry out related experiment exploration from alkynes.Through conditional filtering, at the copper powder of two moles, under the participation of the diethylamine of three moles, in DCE solvent, 70 DEG C of reaction 8h, can obtain the product 3a of alkynyl end trifluoroethyl with the yield of 84%.This reaction does not add amine and does not react, and the effect of the secondary amine of straight chain is preferably as Et
2nH, nPr
2nH, nBu
2nH.And there is the secondary amine of certain steric hindrance or ring-type secondary amine almost can not make reaction occur, primary amine or tertiary amine can not make reaction carry out.And other metal such as Mg, Zn, Fe etc. can not make reaction carry out, CuI, CuBr have to a small amount of product.
Additive is reaction additive: copper powder and amine
afluorine spectrum productive rate;
bdCE represents ethylene dichloride;
ctrifluorobichloroethane makes solvent;
ddiallylamine represents diallyl amine;
erepresent N, N`-dimethyl-ethylenediamine;
fby product is had in product
grepresent Tetramethyl Ethylene Diamine;
Under above-mentioned optimal conditions, the universality of reaction substrate is investigated.This reaction has good suitability to alkyl alkynes and aryl alkynes.As containing to the aryl alkynes of electron substituent group or halogen substiuted, by the time outstanding in productive rate, be wherein CF to bromobenzene acetylene with to the reaction solvent of chlorobenzene acetylene
3cHCl
2.For containing double bond, hydroxyl, thioether, ether, uncle is amino, and the alkyl alkynes of ester group group also can obtain outstanding productive rate.It is worthy of note that this reaction can be amplified.
Additive is reaction additive: the copper powder of 2 molar weights, the diethylamine of 3 molar weights, ethylene dichloride is solvent
The copper that method of the present invention is cheap and diethylamine achieve the linked reaction of alkynes and chloro-1,1, the 1-Halothane of 2,2-bis-in DCE solvent.Reaction conditions is fairly simple, easy handling, can be used for synthesizing the alkynes that a series of trifluoroethyl replaces.Also can obtain higher productive rate, be a kind of potential method solving fluorohaloparaffin and pollute.
Embodiment
Following examples contributes to understanding the present invention, but the present invention is not merely confined in the scope of following example.
Embodiment 1
The reaction conditions adopted except indicating in an embodiment: in the tube sealing of 5ml, adds the copper powder of 0.128g activation, displacement nitrogen 3 times, under inflated with nitrogen, open bottle stopper, add 2mlDCE solvent fast successively, 0.219g diethylamine, 0.102gZ replaces alkynes and 0.306g2, chloro-1,1, the 1-Halothane of 2-bis-, tighten stopper, heat 8 hours in 70 DEG C of oil baths.Leave standstill cooling, with petroleum ether extraction, filter, revolve excess of solvent with water pump decompression, obtain product through column chromatography for separation.
Change the product analytical data that different Z replaces alkynes
4,4,4-, tri-fluoro-ethyl acetylene base benzene (3a)
Productive rate Yield:77%; 142mg; Yellow liquid; Known compound (Ma, J.-A.Angew.Chem.Int.Ed.2012,51,6227.);
1hNMR (300MHz, CDCl
3) δ 7.43-7.47 (m, 2H), 7.25-7.33 (m, 3H), 3.27 (q, J=10.0Hz, 2H);
19fNMR (376MHz, CDCl
3) δ-66.5 (t, J=9.6Hz, 3F);
1-methyl-4-(the fluoro-ethyl acetylene base of 4,4,4-tri-) benzene (3b)
Yield:74% (adopts 3.0 moles of Cu powder and CF
3cHCl
2, DCE is as organic solvent); 146mg; Yellow liquid; Known compound (Ma, J.-A.Angew.Chem.Int.Ed.2012,51,6227.);
1hNMR (300MHz, CDCl
3) δ 7.33 (d, J=7.8Hz, 2H), 7.11 (d, J=7.8Hz, 2H); 3.25 (q, J=9.6Hz, 2H), 2.34 (s, 3H);
19fNMR (282MHz, CDCl
3) δ-66.9 (t, J=9.8Hz, 3F);
1-methoxyl group-4-(the fluoro-ethyl acetylene base of 4,4,4-tri-) benzene (3c)
Yield:73%; 156mg; Yellow liquid; Known compound (Ma, J.-A.Angew.Chem.Int.Ed.2012,51,6227.);
1hNMR (300MHz, CDCl
3) δ 7.37 (d, J=8.7Hz, 2H), 6.82 (d, J=8.7Hz, 2H); 3.78 (s, 3H), 3.24 (q, J=9.6Hz, 2H);
19fNMR (282MHz, CDCl
3) δ-66.9 (t, J=10.0Hz, 3F);
The 1-tertiary butyl-4-(the fluoro-ethyl acetylene base of 4,4,4-tri-) benzene (3d)
Yield:55%; 132mg; Colourless liquid; Known compound (Szabo, K.J.Org.Lett.2012,14,3966.);
1hNMR (300MHz, CDCl
3) δ 7.37 (m, 4H), 3.26 (q, J=9.5Hz, 2H), 1.32 (s, 9H);
19fNMR (282MHz, CDCl
3) δ-66.9 (t, J=9.8Hz, 3F);
The fluoro-4-of 1-(the fluoro-ethyl acetylene base of 4,4,4-tri-) benzene (3e)
Yield:50%; 101mg; Yellow liquid; Known compound (Ma, J.-A.Angew.Chem.Int.Ed.2012,51,6227.);
1hNMR (300MHz, CDCl
3) δ 7.40-7.45 (m, 2H), 6.97-7.03 (m, 3H), 3.25 (q, J=9.6Hz, 2H);
19fNMR (282MHz, CDCl
3) δ-66.8 (t, J=9.8Hz, 3F) ,-110.6 (m, 1F);
The chloro-4-of 1-(the fluoro-ethyl acetylene base of 4,4,4-tri-) benzene (3f)
Yield:38% (CF
3cHCl
2as organic solvent); 82mg; Colourless liquid; Known compound (Shibata, M.Chem.Commun.2013,49,7809.);
1hNMR (300MHz, CDCl
3) δ 7.37 (d, J=8.1Hz, 2H), 7.28 (d, J=8.4Hz, 2H), 3.26 (q, J=9.4Hz, 2H);
19fNMR (282MHz, CDCl
3) δ-66.8 (t, J=8.8Hz, 3F);
The bromo-4-of 1-(the fluoro-ethyl acetylene base of 4,4,4-tri-) benzene (3g)
Yield:51% (CF
3cHCl
2as organic solvent); 134mg; Yellow liquid; Known compound (Ma, J.-A.Angew.Chem.Int.Ed.2012,51,6227.);
1hNMR (300MHz, CDCl
3) δ 7.43 (d, J=8.7Hz, 2H), 7.29 (d, J=8.7Hz, 2H), 3.25 (q, J=9.5Hz, 2H);
19fNMR (282MHz, CDCl
3) δ-66.7 (t, J=9.8Hz, 3F);
The fluoro-2-of 1-(the fluoro-ethyl acetylene base of 4,4,4-tri-) benzene (3h)
Yield:39%; 82mg; Yellow liquid; New compound;
1hNMR (300MHz, CDCl
3) δ 7.43 (tm, J=6.0Hz, 1H), 7.31 (qm, J=7.0Hz, 1H), 7.07 (q, J=8.0Hz, 2H), 3.31 (q, J=10.0Hz, 2H);
19fNMR (282MHz, CDCl
3) δ-66.8 (t, J=9.8Hz, 3F) ,-110.6 (m, 1F);
13cNMR (100MHz, CDCl
3) δ 162.9 (d, J=251Hz), 133.7,130.4,124.0 (q, J=275Hz), 123.8,115.4 (d, J=21Hz), 110.7 (d, J=16Hz), 82.7 (q, J=5Hz), 77.8,27.9; IR (neat) ν/cm
-1: 2936.3,1614.0,1578.8,1493.9,1450.7,1419.7,1366.1,1281.7,1259.7,1219.6,1150.7,1111.4,1032.3,906.6,822.4,756.9,659.2; EI-MSm/z (%): 107 (3), 133 (63), 134 (6), 151 (8), 182 (17), 183 (12), 202 (100), 203 (11); HRMS-EI (M
+) calculated value CalcdforC
10h
6f
4: 202.0406; Measured value found:202.0407;
1-(the fluoro-1-alkynes of 4,4,4-tri--1-butyl) tetrahydrobenzene (3i)
Yield:75%; 141mg; Yellow liquid; New compound;
1hNMR (300MHz, CDCl
3) δ 6.13 (s, 1H), 3.14 (q, J=10.0Hz, 2H), 2.08-2.10 (m, 4H), 1.55-1.64 (m, 4H);
19fNMR (282MHz, CDCl
3) δ-67.3 (t, J=8.5Hz, 3F);
13cNMR (100MHz, CDCl
3) δ 135.3,124.4 (q, J=275Hz), 119.3,85.5,74.0 (q, J=5Hz), 28.4,26.1 (q, J=34Hz), 25.0,21.6,20.8; IR (neat) ν/cm
-1: 2934.1,2862.5,2236.9,1650.5,1450.1,1370.4,1254.9,1146.7,1111.1,906.9,841.5,671.3,589.7; EI-MSm/z (%): 77 (26), 91 (90), 105 (66), 109 (23), 119 (24), 173 (41), 174 (30), 188 (100); HRMS-EI (M
+) CalcdforC
10h
11f
3: 188.0813; Found:188.0817;
1,1,1-trifluorododecyl-3-alkynes (3j)
Yield:89%; 1.96g; Yellow liquid; New compound; ;
1hNMR (300MHz, CDCl
3) δ 3.00 (qm, J=9.0Hz, 2H), 2.13-2.19 (m, 2H), 1.47-1.52 (q, J=9.0Hz, 2H), 1.27-1.35 (m, 10H), 0.88 (t, J=9.0Hz, 2H);
19fNMR (282MHz, CDCl
3) δ-67.5 (t, J=9.8Hz, 3F);
13cNMR (100MHz, CDCl
3) δ 124.4 (q, J=275Hz), 84.9,68.0 (q, J=5Hz), 31.7,29.1,28.9,28.7,28.3,26.0 (q, J=34Hz), 22.6,18.4,13.9; IR (neat) ν/cm
-1: 2930.6,2858.4,1642.8,1493.9,1468.4,1422.0,1357.2,1257.8,1157.9,1139.6,1112.9,908.8,834.4,656.3; Anal.calcdforC
12h
19f
3: C65.43, H8.69; Found:C65.50, H8.70;
The fluoro-7-of 1,1,1-tri-(rare-1-pentyloxy of 4-)-3-heptyne (3k)
Yield:77%; 180mg; Yellow liquid; New compound; ;
1hNMR (400MHz, CDCl
3) δ 5.79-5.84 (m, 1H), 4.95-5.05 (m, 2H), 3.49 (t, J=8.0Hz, 2H), 3.44 (t, J=8.0Hz, 2H), 3.00 (qm, J=9.4Hz, 2H), 2.28-2.30 (m, 2H), (2.12 m, 2H), 1.75-1.79 (m, 2H), 1.65-1.69 (m, 2H);
19fNMR (376MHz, CDCl
3) δ-67.2 (t, J=9.4Hz, 3F);
13cNMR (100MHz, CDCl
3) δ 138.3,124.9 (q, J=275Hz), 114.6,84.3,70.2,68.9,68.4 (q, J=5Hz), 30.3,28.8,28.6,26.1 (q, J=34Hz), 16.3; IR (neat) ν/cm
-1: Anal.calcdforC
13h
19f
3o:C61.53, H7.31, F24.33; Found:C61.51, H7.30, F24.05;
The fluoro-4 heptyne-1-alcohol (3l) of 7,7,7-tri-
Yield:71%; 117mg; Yellow liquid; New compound; ;
1hNMR (300MHz, CDCl
3) δ 3.74 (t, J=6.0Hz, 2H), 3.00 (qm, J=9.4Hz, 2H), 2.29-2.35 (m, 2H), 1.91 (s, 1H), 1.72-1.81 (m, 2H);
19fNMR (282MHz, CDCl
3) δ-67.4 (m, 3F);
13cNMR (100MHz, CDCl
3) δ 124.3 (q, J=275Hz), 84.0,68.8 (q, J=5Hz), 61.3,30.9,26.0 (q, J=34Hz), 15.0; IR (neat) ν/cm
-1: 3364.8,2939.7,2246.0,1423.8,1368.4,1282.4,1158.6,1056.2,931.6,833.7,657.0; EI-MSm/z (%): 69 (14), 79 (34), 97 (22), 83 (23), 101 (15), 127 (12), 148 (100), 165 (6); HRMS-EI (M-1) CalcdforC
7h
8oF
3: 165.0527; Found:165.0522;
(4-p-methoxy-phenyl) (the fluoro-4-alkynes of 7,7,7-tri--1-heptyl) thioether (3m)
Yield:68%; 196mg; Yellow liquid; New compound;
1hNMR (400MHz, CDCl
3) δ 7.37 (d, J=8.0Hz, 2H), 6.87 (d, J=8.0Hz, 2H), (3.82 s, 2H), 3.01 (qm, J=9.4Hz, 2H), 2.93 (t, J=8.0Hz, 2H), 2.33-2.37 (m, 2H), 1.77-1.80 (m, 2H);
19fNMR (376MHz, CDCl
3) δ-66.9 (t, J=9.4Hz, 3F);
13cNMR (100MHz, CDCl
3) δ 159.0,133.3,126.0,124.4 (q, J=275Hz), 114.6,83.8,69.04 (q, J=5Hz), 55.31,34.6,27.9,26.1 (q, J=34Hz), 17.4; IR (neat) ν/cm
-1: 3003.5,2940.0,2837.8,1593.4,1494.5,1441.8,1366.8,1283.1,1140.8,1032.3,908.0,828.4,798.9; EI-MSm/z (%): 95 (17), 108 (18), 109 (19), 125 (34), 139 (64), 140 (100), 153 (17), 288 (32); HRMS-EI (M
+) CalcdforC
14h
15oF
3s:288.0796; Found:288.0797;
(the fluoro-4-alkynes of 7,7,7-tri--1-oxygen in heptan base)-benzene (3n)
Yield:83%; 200mg; Yellow liquid; New compound;
1hNMR (400MHz, CDCl
3) δ 7.33 (t, J=8.0Hz, 2H), 6.94-7.01 (m, 3H), 4.01 (d, J=8.0Hz, 2H), 3.01-3.08 (qm, J=9.4Hz, 2H), 2.43-2.47 (m, 2H), 2.00-2.07 (m, 2H);
19fNMR (376MHz, CDCl
3) δ-66.9 (t, J=9.4Hz, 3F);
13cNMR (100MHz, CDCl
3) δ 159.9,129.4,124.4 (q, J=275Hz), 120.7,114.5,83.9,68.9 (q, J=5Hz), 66.0,28.2,26.1 (q, J=34Hz), 15.3; IR (neat) ν/cm
-1: 3063.8,2937.2,1600.8,1497.8,1367.0,1246.9,1138.7,1053.8,946.9,908.1,832.8; EI-MSm/z (%): 51 (6), 65 (10), 77 (15), 85 (6), 94 (100), 95 (9), 101 (6), 242 (14); HRMS-EI (M
+) CalcdforC
13h
13oF
3: 242.0918; Found:242.0914;
N-methyl-N-(the fluoro-4-alkynes of 7,7,7-tri--1-heptyl) aniline (3o)
Yield:94%; 240mg; Yellow liquid; New compound;
1hNMR (400MHz, CDCl
3) δ 7.29-7.83 (m, 1H), 6.76-6.82 (m, 1H), 3.50 (t, J=8.0Hz, 2H), 3.08 (qm, J=9.4Hz, 2H), 3.01 (s, 3H), 2.30-2.32 (m, 2H), 1.83-1.90 (m, 2H);
19fNMR (376MHz, CDCl
3) δ-66.9 (t, J=9.4Hz, 3F);
13cNMR (100MHz, CDCl
3) δ 149.3,129.2,124.5 (q, J=275Hz), 116.3,112.3,84.3,69.0 (q, J=5Hz), 51.5,38.4,26.2 (q, J=34Hz), 25.6,16.2; IR (neat) ν/cm
-1: 3094.3,3062.4,2936.7,1600.5,1506.2,1450.9,1366.3,1280.5,1138.4,1034.0,991.5,907.7,832.9; ESI-MSm/z (%): 255.9 (M+1); HRMS-ESI (M+H) CalcdforC
14h
17nF
3: 256.1308; Found:256.1314;
The fluoro-4-alkynes of 7,7,7-tri--1-heptyl benzoate (3p)
Yield:84%; 225mg; Yellow liquid; New compound;
1hNMR (300MHz, CDCl
3) δ 8.05 (d, J=6.0Hz, 2H), 7.56 (t, J=7.5Hz, 1H), 7.44 (t, J=7.5Hz, 2H), 4.41 (t, J=6.0Hz, 2H), 3.00 (qm, J=10.0Hz, 2H), 2.36-2.42 (m, 2H), (1.94-2.04 t, J=6.0Hz, 2H);
19fNMR (282MHz, CDCl
3) δ-67.3 (t, J=9.8Hz, 3F);
13cNMR (100MHz, CDCl
3) δ 166.4,132.9,130.1,129.5,128.3,124.3 (q, J=275Hz), 83.4,69.1 (q, J=5Hz), 63.4,27.6,26.0 (q, J=34Hz), 15.5; IR (neat) ν/cm
-1: 3064.7,2963.7,1720.6,1602.5,1452.4,1388.5,1274.0,1111.6,1027.6,908.4,833.1,712.1; EI-MSm/z (%): 51 (12), 77 (43), 79 (17), 105 (100), 106 (8), 123 (9), 148 (29), 269 (7); HRMS-EI (M-1) CalcdforC
14h
12o
2f
3: 269.0789; Found:269.0790.
Embodiment 2
When phenylacetylene is reactant, adopt the embodiment of solvent C F3CHCl2: in the tube sealing of 5ml, add the copper powder of 0.128g activation, displacement nitrogen 3 times, under inflated with nitrogen, opens bottle stopper, add 2mlCF3CHCl2 successively fast and do reactant and solvent, 0.219g diethylamine and 0.102g phenylacetylene, tighten stopper, heats 8 hours in 70 DEG C of oil baths.Leave standstill cooling, with petroleum ether extraction, filter, revolve excess of solvent with water pump decompression, obtain product 3a92mg through column chromatography for separation, productive rate 50%.
Embodiment when phenylacetylene is reactant, differing temps: in the tube sealing at 5ml, adds the copper powder of 0.128g activation, displacement nitrogen 3 times, under inflated with nitrogen, opens bottle stopper, add 2mlDCE solvent fast successively, 0.219g diethylamine, 0.102g phenylacetylene and 0.306g2,2-bis-chloro-1,1,1-Halothane, tightens stopper, heats 8 hours in 60 DEG C of oil baths.Leave standstill cooling, with petroleum ether extraction, filter, revolve excess of solvent with water pump decompression, obtain product 3a62mg through column chromatography for separation, productive rate 34%.
When phenylacetylene is reactant, change the embodiment of material ratio: in the tube sealing of 5ml, add the copper powder of 0.256g activation, displacement nitrogen 3 times, under inflated with nitrogen, opens bottle stopper, add 2mlDCE solvent fast successively, 0.292g diethylamine, 0.102g phenylacetylene and 0.153g2,2-bis-chloro-1,1,1-Halothane, tightens stopper, heats 8 hours in 70 DEG C of oil baths.Leave standstill cooling, with petroleum ether extraction, filter, revolve excess of solvent with water pump decompression, obtain product 3a99mg through column chromatography for separation, productive rate 54%.
Embodiment when phenylacetylene is reactant, different amine: in the tube sealing at 5ml, adds the copper powder of 0.128g activation, displacement nitrogen 3 times, under inflated with nitrogen, opens bottle stopper, add 2mlDCE solvent fast successively, 0.303g di-n-propylamine, 0.102g phenylacetylene and 0.306g2,2-bis-chloro-1,1,1-Halothane, tightens stopper, heats 8 hours in 60 DEG C of oil baths.Leave standstill cooling, with petroleum ether extraction, filter, revolve excess of solvent with water pump decompression, obtain product 3a90mg through column chromatography for separation, productive rate 49%.
Claims (5)
1. prepare the method for Fluoroacetylenes using alkynes as nucleophilic reagent and chloro-1,1, the 1-Halothane generation linked reaction of 2,2-bis-for one kind, to it is characterized in that in polar organic solvent and 55 DEG C ~ 90 DEG C time, at two (C
2-C
8alkyl) amine, two (C
2-C
4thiazolinyl) under amine, N, N`-dimethyl-ethylenediamine or Tetramethyl Ethylene Diamine exist, the cuprous or Z of alkynyl replaces alkynes, chloro-1,1, the 1-Halothane of 2,2-bis-and copper powder linked reaction 1 ~ 10 hour; Cuprous or the substituent alkynes of Z of described alkynyl, chloro-1,1, the 1-Halothane of 2,2-bis-, copper powder, two (C
2-C
8alkyl) amine, two (C
2-C
4thiazolinyl) mol ratio of amine, N, N`-dimethyl-ethylenediamine or Tetramethyl Ethylene Diamine is followed successively by: 1:0.5-20:0.5-5:1-5; Described Z substituting group is C
1-C
12alkyl, aryl, containing to the aryl of electron substituent group or halogen substiuted, the C containing double bond, hydroxyl, thioether, ether, alkene alkoxyl group, tertiary amine groups or ester group group
3-C
24base; Described aryl is phenyl or naphthyl.
2. the method for claim 1, is characterized in that two described (C
2-C
8alkyl) amine or two (C
2-C
4thiazolinyl) amine is diethylamine, diallyl amine.
3. the method for claim 1, is characterized in that described Z is preferably C
2-C
12alkyl C
4-C
8cycloalkenyl group, C
1-C
12the C that alkoxyl group replaces
2-C
12alkyl, C
2-C
6the C of alkenyl substituted
1-C
12alkyl, phenyl, the phenyl that R replaces, C
1-C
12alkylthio C
2-C
12alkyl, arylthio C
2-C
12alkyl, methoxyphenyl sulfo-C
1-C
6alkyl, N-C
1-C
8the tertiary amine C of alkyl
1-C
8alkyl, C
1-C
4alkyl carboxylic acid C
2-C
12carbalkoxy or fragrant C
1-C
4alkyl carboxylic acid C
2-C
12carbalkoxy
;wherein R is halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group.
4. the method for claim 1, is characterized in that described organic polar solvent is methylene dichloride, 1,2-ethylene dichloride, acetonitrile or chloro-1,1, the 1-Halothane of 2,2-bis-.
5. the method for claim 1, is characterized in that described product is by organic solvent extraction, filtration, distillation removing excess of solvent or through column chromatographic isolation and purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410770656.1A CN104557448B (en) | 2014-12-15 | 2014-12-15 | The method of Fluoroacetylenes is prepared with alkynes and chloro-1,1, the 1-Halothane generation linked reaction of 2,2-bis- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410770656.1A CN104557448B (en) | 2014-12-15 | 2014-12-15 | The method of Fluoroacetylenes is prepared with alkynes and chloro-1,1, the 1-Halothane generation linked reaction of 2,2-bis- |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104557448A CN104557448A (en) | 2015-04-29 |
| CN104557448B true CN104557448B (en) | 2016-04-13 |
Family
ID=53074633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410770656.1A Expired - Fee Related CN104557448B (en) | 2014-12-15 | 2014-12-15 | The method of Fluoroacetylenes is prepared with alkynes and chloro-1,1, the 1-Halothane generation linked reaction of 2,2-bis- |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104557448B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4786876B2 (en) * | 2004-03-10 | 2011-10-05 | ダイセル化学工業株式会社 | Method for producing alkynes |
-
2014
- 2014-12-15 CN CN201410770656.1A patent/CN104557448B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104557448A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10703694B2 (en) | Method of manufacturing 1-chloro-2,3,3-trifluoropropene | |
| EP2785671B1 (en) | Process for the production of chlorinated propanes | |
| EP2066604B1 (en) | Dehydrofluorination process to manufacture hydrofluoroolefins | |
| US6207864B1 (en) | Process for preparing cyclopropylacetylene | |
| WO2010087117A1 (en) | Method for producing dichloropyrazine derivative | |
| JP6008205B2 (en) | Industrial production method of arylsulfapentafluoride | |
| CN104557358A (en) | Alkyl trifluoromethyl thioether compound and preparation method thereof | |
| KR102371155B1 (en) | A method to produce 1,1,2,3-tetrachloropropene with high yield | |
| CN104557448B (en) | The method of Fluoroacetylenes is prepared with alkynes and chloro-1,1, the 1-Halothane generation linked reaction of 2,2-bis- | |
| US20080319238A1 (en) | Process for Production of Biphenyl Derivatives | |
| JP3459892B2 (en) | Fluorinated surfactant compound and method for producing the same | |
| JP5736201B2 (en) | Method for producing 2,3-dichloropyridine | |
| CN101331113A (en) | Process for the preparation of 2-chloroethoxy-acetic acid-N,N-dimethylamide | |
| WO2010121098A1 (en) | Improved process for the preparation of halo-olefins | |
| JP6894608B2 (en) | New Cyclic Urea Derivative-Hydrogen Bromide | |
| JP2007145811A (en) | Method for producing biphenyl derivative | |
| JP5803420B2 (en) | Process for producing β, β-difluoro-α, β-unsaturated carbonyl compound | |
| JPS6335548A (en) | Production of triarylamine | |
| JP2004161703A (en) | Method for producing 2-fluoro-4-(trifluoromethyl) benzonitrile | |
| JP6039242B2 (en) | Method for producing triarylamines | |
| CN110396037B (en) | Method for preparing octafluoro-2-butene | |
| JP5305321B2 (en) | Method for producing fluoro compound | |
| JP4518247B2 (en) | Method for producing α, α-difluoromethyl compound | |
| CN108026005B (en) | Homoallylic halide composition and method for preserving homoallylic halide | |
| EP1000929B1 (en) | Process for preparing o-nitrobenzonitriles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160413 Termination date: 20191215 |