CN1200717A - Process for preparing 4-bromo-1,1-difluorbut-1-ene and 2,4-dibromo-1,1,1-trifluorobutane - Google Patents

Process for preparing 4-bromo-1,1-difluorbut-1-ene and 2,4-dibromo-1,1,1-trifluorobutane Download PDF

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CN1200717A
CN1200717A CN96197873A CN96197873A CN1200717A CN 1200717 A CN1200717 A CN 1200717A CN 96197873 A CN96197873 A CN 96197873A CN 96197873 A CN96197873 A CN 96197873A CN 1200717 A CN1200717 A CN 1200717A
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bromo
trifluoro butane
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trifluoro
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A·G·威廉姆斯
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Syngenta Ltd
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Zeneca Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/14—Acyclic saturated compounds containing halogen atoms containing fluorine and bromine
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for the preparation of 4-bromo-1,1-difluorobut-1-ene comprising the step of reacting 2,4-dibromo-1,1,1-trifluorobutane with a defluorobrominating agent in a liquid reaction mass and recovering the desired product therefrom. The product is useful as an intermediate for pesticidal compounds.

Description

4-bromo-1,1-difluoro butene-1 and 2,4-two bromo-1,1, the preparation method of 1-trifluoro butane
The present invention relates to prepare 4-bromo-1, the novel method of 1-difluoro butene-1.The present invention also relates to prepare 2,4-two bromo-1,1, the novel method of 1-trifluoro butane.
4-bromo-1,1-difluoro butene-1 in a lot of fields in, aspect agrochemicals and fluoropolymer, be useful compound for example, both can be used as the finished product, can be used as intermediate especially again.
International Patent Application Publication No. WO94/06777, WO94/06782, WO95/24403 and WO96/00003 disclose a series of can be used as nematocides contain 4, the 4-difluoro fourth-substituent Hete rocyclic derivatives of 3-thiazolinyl sulfo-, and preparation method thereof.These methods relate to and 4-bromo-1, the step of 1-difluoro butene-1 reaction.Someone proposes by bromizate hydrogen and commercial compound 4-bromo-1,1 under the standard conditions of addition reaction, and 2-trifluoro butene-1 reacts and prepares 4-bromo-1,1-difluoro butene-1.For example, randomly in the presence of free-radical generating agent, bromizate hydrogen by 4-bromo-1,1, the solution of 2-trifluoro butene-1 in inert solvent, make 1,4-two bromo-1,1,2-trifluoro butane, handle this compound with the agent of debrominate fluorine then, just made 4-bromo-1,1-difluoro butene-1.
The present invention relates to prepare 4-bromo-1, therefore improving one's methods of 1-difluoro butene-1 also relate to 4-bromo-1, and 1-difluoro butene-1 prepares improving one's methods of final product as intermediate.The advantage of the inventive method is to avoid using hazardous agents, as HF and LiAlHF.
According to one aspect of the present invention, a kind of preparation 4-bromo-1 is provided, the method for 1-difluoro butene-1, this method comprises makes 2, and 4-two bromo-1,1,1-trifluoro butane react with a kind of defluorinate bromide in liquid reaction medium, and from wherein reclaiming the step of required product.
The liquid reaction medium preferably water, polarity irreducibility liquid that can be miscible with water, as methyl alcohol and DMF, or their mixture.
Preferred defluorinate bromide comprises zinc, magnesium and aluminium.Especially preferred zinc.Yet scope of the present invention is not limited to use metal as the defluorinate bromide, and other technology also can be used as electrochemistry defluorinate chlorine technology, and be to belong within the scope of the present invention.
When using metal, preferably using at least, the defluorinate bromide of stoichiometry reacts.More preferably every mole 2,4-two bromo-1,1,1-trifluoro butene-1 uses the about 1.5 moles of defluorinate bromides of about 1.2-.Yet, when this process is carried out with electrochemical means, can use defluorinate bromide less than stoichiometry.
This reaction is preferably being carried out under about 1 normal atmosphere and under up to about 100 ℃ temperature.
A kind of initiator of preferred use starts reaction.The initiator that is suitable for comprises iodine, concentrated hydrochloric acid or even from the kish that reacts previously.
According to another aspect of the present invention, a kind of preparation 4-bromo-1 is provided, the method for 1-difluoro butene-1, this method comprises the following steps:
(a) make 1,1,1-trifluoro butane-2,4-sulphonate (wherein this sulfonate radical is a leavings group) and a kind of bromide source reaction generate 2,4-two bromo-1,1,1-trifluoro butane; With
(b) make 2,4-two bromo-1,1,1-trifluoro butane and a kind of defluorinate bromide react in liquid reaction medium.
In step (a), preferred tosylate of sulphonate or methanesulfonates.Be reflected under about 1 normal atmosphere and preferably at least about 100 ℃,, even more preferably under about 130 ℃-Yue 200 ℃ temperature, carry out more preferably at about 130 ℃-Yue 250 ℃.
This reaction is preferably at polar aprotic solvent, as carrying out in tetrahydrofuran (THF), dimethyl formamide, N-Methyl pyrrolidone, methane amide, tetramethylene sulfone and the ketone equal solvent.
Preferably a kind of neutral bromide source of bromide source, it should be able to be dissolved in and be fit to carry out in the solvent of this reactions steps, alkali metal bromide for example, as lithiumbromide, Sodium Bromide or Potassium Bromide, Calcium Bromide, bromination quaternary ammonium and bromination season pyrimidine.
According to another aspect of the present invention, a kind of preparation 4-bromo-1 is provided, the method for 1-difluoro butene-1, this method comprises the following steps:
(a) make 1,1,1-trifluoro butane-1, the reaction of 2-glycol and a kind of sulfonic acid halide, generate corresponding 1,1,1-trifluoro butane-2,4-sulphonate;
(b) make 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1,1-trifluoro butane; With
(c) make 2,4-two bromo-1,1,1-trifluoro butane and a kind of defluorinate bromide react in liquid reaction medium.
In step (a), sulphonate is tosylate or the methanesulfonates that obtains by with suitable SULPHURYL CHLORIDE reaction.
This reaction is preferably carried out in the presence of solvent.Preferably a kind of polar aprotic solvent of solvent, those solvents as mentioned above.
This reaction is lower than under the boiling point of selected solvent and about 1 normal atmosphere more fortunately to be carried out.
In a preferred specific embodiments, be reflected under the existence of alkali and carry out, preferred organic bases is as tertiary amine.Although do not wish to be bound by any theory, can think that alkali helps to form the alkoxyl group kind.
According to another aspect of the present invention, a kind of preparation 4-bromo-1 is provided, the method for 1-difluoro butene-1, this method comprises the following steps:
(a) make the reaction of trifluoromethyl ethanoyl ethyl acetate and borohydride, generate 1,1,1-trifluoro butane-1,2-glycol;
(b) make 1,1,1-trifluoro butane-1, the reaction of 2-glycol and a kind of sulfonic acid halide, generate corresponding 1,1,1-trifluoro butane-2,4-sulphonate;
(c) make 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1,1-trifluoro butane; With
(d) make 2,4-two bromo-1,1,1-trifluoro butane and a kind of defluorinate bromide react in liquid reaction medium.
Step (a) can be by J.Flurine Chem. (1982), and 20, method described in the 301-306 is carried out, and still, we find that the consumption of borohydride can lack than the consumption described in the document.What know is that this is favourable for environment protection.
In step (a), the preferred sodium borohydride of borohydride, reaction is carried out in those solvents for example above-mentioned preferably at polar aprotic solvent.Used solvent must not can be reduced by borohydride.
As previously mentioned, the invention still further relates to preparation 2,4-two bromo-1,1, the method for 1-trifluoro butane.
People such as Misani are at J.Am.Chem.Soc., and (1956), 78, narrated among the 2801-2804 by making 1,1,1-trifluoro butane-2,4-glycol and phosphorus tribromide react and prepare 2,4-two bromo-1,1, the trial of the failure of 1-trifluoro butane.2,4-two bromo-1,1,1-trifluoro butane is actually by Beta-bromo-γ, γ, γ-trifluoroacetic acid ethyl ester and 1,1, the preparation of 1-three fluoro-2-bromo-4-butanols (reaction).According to people such as Vasileva at Izv.Akad.Nauk.SSSR, SerKhim, 1989 (11), report says 2,4-two bromo-1,1 among the 2558-62,1-trifluoro butane be with by methylene bromide and 3,3, other product that 3-trifluoro propene-1 reaction is generated is together that form of mixtures makes.Yet these methods have all been used harmful or return volatile reactants.
Therefore,, provide a kind of preparation 2 according to one aspect of the present invention, 4-two bromo-1,1, the method for 1-trifluoro butane, this method comprises the following steps:
(a) make 1,1,1-trifluoro butane-2,4-sulphonate (wherein sulfonate radical is a leavings group) and a kind of bromide source reaction generate 2,4-two bromo-1,1,1-trifluoro butane.
According to another aspect of the present invention, a kind of preparation 2 is provided, 4-two bromo-1,1, the method for 1-trifluoro butane, this method comprises the following steps:
(a) make 1,1,1-trifluoro butane-1, the reaction of 2-glycol and a kind of sulfonic acid halide, generate corresponding 1,1,1-trifluoro butane-2,4-sulphonate; With
(b) make 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1,1-trifluoro butane.
According to another aspect of the present invention, a kind of preparation 2 is provided, 4-two bromo-1,1, the method for 1-trifluoro butane, this method comprises the following steps:
(a) make the reaction of trifluoromethyl-ethanoyl ethyl acetate and borohydride, generate 1,1,1-trifluoro butane-1,2-glycol;
(b) make 1,1,1-trifluoro butane-1, the reaction of 2-glycol and a kind of sulfonic acid halide, generate corresponding 1,1,1-trifluoro butane-2,4-sulphonate; With
(c) make 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1,1-trifluoro butane.
What know is, that is mentioned prepares 4-bromo-1 with the present invention, and the relevant preferred feature of the method for 1-difluoro butene-1 is applicable to that all the present invention prepares 2,4-two bromo-1,1, the corresponding steps in the method for 1-trifluoro butane.
Mode with limiting examples illustrates various preferred feature of the present invention and specific embodiments with reference to following example now.
Example 1
This example explanation 1,1,1-trifluoro butane-2, the preparation of 4-glycol.
17.2g sodium borohydride at room temperature is suspended in the 400ml tetrahydrofuran (THF), drips 64g trifluoromethyl ethanoyl ethyl acetate with 100 fens clock times.Reaction mixture during dripping is because heat release reaches 40 ℃.Mixture refluxed 2.5 hours, was cooled to 50 ℃ then.Then add 240ml methyl alcohol, slowly add during beginning, emit the reduction of speed then along with hydrogen, can quickerly add to avoid forming foam.Then reactant was refluxed 1 hour again, steam the 250ml overhead product, the solvent cumulative volume is reduced.Mixture is cooled to room temperature.Add 400ml water and 75ml ether, then stir.Separate water, use 3 * 75ml extracted with diethyl ether again.The combined ether extract is used dried over mgso, and vapourisation under reduced pressure then obtains the viscous liquid of the shallow straw yellow of 33g, contains 77% purpose product through the GLC analysis revealed.
NMR:CF 3CH (multiplet, 4.2ppm); OHCH 2(multiplet, 1.85ppm);
CH 2(multiplet, 3.9ppm)
[annotate: at CDCl 3Middle OH proton can not clearly be distinguished]
19F NMR:CF 3(unimodal ,-81ppm).
Example 2
This example explanation l, 1,1-trifluoro butane-2, the preparation of 4-pair-p-toluenesulfonic esters
32g is thick 1,1, and 1-trifluoro butane-2,4-glycol join in the 100ml tetrahydrofuran (THF) with the 51.7g Tosyl chloride and make soup compound.Drip the 45g triethylamine with 45 fens clock times and make reaction mixture heat release to 35 ℃ and retrogradation.The GLC monitoring shows that 6 hours afterreactions are still incomplete.In subsequently 13 days, add other 2.0g Tosyl chloride in batches.GLC analysis revealed reactive material is the mixture of purpose product (60%), monohydroxy tosylate (10%) and 2-chloro-4-tosylate (10%).Reactive material is mixed with the 300ml ether, filter then.Filter cake washs with tetrahydrofuran (THF).Obtain 86g viscosity amber oil behind the filtrate vapourisation under reduced pressure.This oil of 76g is dissolved in the methylene dichloride, washes with water.Obtain the 43g crude product after the mixture drying.GLC MS analysis revealed main peak is 1,1 of Mwt 452,1-trifluoro butane-2,4-pair-p-toluenesulfonic esters.Also detect 1,1 of a spot of Mwt316,1-three fluoro-Sec-Butyl Chloride-4-tosylate.
NMR：7.85(D)，7.75(D)，7.40(D)，7.35(D)，4.95(CM)，
4.18(CM)，4.05(CM)，2.45(S)，2.45(S)，2.20(CM)，
2.08(CM)。
19F?NMR：-77.28(S)
Example 3
This example explanation 2,4-two bromo-1,1, the preparation of 1-trifluoro butane
Lithiumbromide is joined in the 120ml N-Methyl pyrrolidone, and be heated to 100 ℃, form a kind of solution, this solution is cooled to 70 ℃, add the 40ml dehydrated alcohol then.Then this mixture is reheated to 218 ℃, distill out 40ml ethanol and minor amount of water simultaneously.Allow mixture be cooled to 80 ℃, add the 30ml hexanaphthene.With mixture heating up to 218 ℃, collect overhead product simultaneously again.Allow mixture cooling, add good thick 1,1 of prepared beforehand with 30 fens clock times, 1-trifluoro butane-2, washes by means of 2 * 20ml N-crassitude by 4-pair-p-toluenesulfonic esters.After room temperature was through 1 hour, mixture is carried out GLC and analyze, show that all two-tosylate all changes into 4-bromo-2-tosylate.With about 2 hours of mixture heating up to 90 ℃ maintenance, make it be cooled to ambient temperature overnight then.The GLC analysis revealed is not transformed into product fully.With mixture heating up to 130 ℃, kept 5 hours, at this moment the end of term, just think to react completely.Allow reactive material be cooled to room temperature, pour in the water then.Water extracts with 3 * 100ml, 30/40 gasoline ether.Organic extract washes with water 1 time, uses dried over sodium sulfate, removes whole gasoline ethers with flash method under normal pressure, and the top temperature reaches 40 ℃.The cut below 50 ℃ is collected in residue water pump underpressure distillation.Mixture output 6.8g, GLC analysis revealed contain product (78%) and 2-bromo-4-chloro-1,1,1-trifluoro butane (9.4%).
Product is identified by GLC MS: product: Mwt268; Bromine chlorine: Mwt224.
NMR：CH(CM4.4ppm)；BrCH 2(CM2.3ppm；CM2.5ppm)；
CH 2(M3.5ppm；M3.6ppm)Br。
19F?NMR：CF 3(S-72.52ppm)。
Example 4
This example explanation 4-bromo-1, the preparation of 1-difluoro butene-1
2.7g 2,4-two bromo-1,1,1-trifluoro butane join in the flask that contains 5ml water and 0.8g zinc metal powder.With this mixture heating up to 70 ℃, and add 2 concentrated hydrochloric acids and crystallization iodine with initiation reaction.After 90 minutes, show that with GLC analysis monitoring reaction process reaction stops at 70 ℃.Need add 0.2g zinc metal powder again and continue heating 90 minutes again for making to react completely.Reaction flask is dressed up water distilling apparatus so that distill, and heat temperature raising is collected 65-100 ℃ overhead product.Overhead product obtains after with a small amount of dried over sodium sulfate: 0.95g crude product (GLC analyzes 73.8%), and product is identified by GLC MS: product Mwt172; Add a spot of 4-chloro-1,1-difluoro butene-1, Mwt128.
NMR:BrCH 2(triplet, 3.37ppm); CH 2(multiplet, 2.55ppm);
CH (multiplet, 4.28ppm)
19F：CF 2(D-87.37，-87.43ppm)；(d-89.17；-89.17ppm)。

Claims (8)

1. one kind prepares 4-bromo-1, the method for 1-difluoro butene-1, and this method comprises makes 2, and 4-two bromo-1,1,1-trifluoro butane react with a kind of defluorinate bromide in liquid reaction medium, and from wherein reclaiming the step of required product.
2. preparation 4-bromo-1 according to claim 1, the method for 1-difluoro butene-1, this method comprises the following steps:
(a) make 1,1,1-trifluoro butane-2,4-sulphonate (wherein this sulfonate radical is a leavings group) and a kind of bromide source reaction generate 2,4-two bromo-1,1,1-trifluoro butane; With
(b) make 2,4-two bromo-1,1,1-trifluoro butane and a kind of defluorinate bromide react in liquid reaction medium.
3. preparation 4-bromo-1 according to claim 1, the method for 1-difluoro butene-1, this method comprises the following steps:
(a) make 1,1,1-trifluoro butane-1, the reaction of 2-glycol and a kind of sulfonic acid halide, generate corresponding 1,1,1-trifluoro butane-2,4-sulphonate;
(b) make 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1,1-trifluoro butane; With
(c) make 2,4-two bromo-1,1,1-trifluoro butane and a kind of defluorinate bromide react in liquid reaction medium.
4. preparation 4-bromo-1 according to claim 1, the method for 1-difluoro butene-1, this method comprises the following steps:
(a) make the reaction of trifluoromethyl ethanoyl ethyl acetate and borohydride, generate 1,1,1-trifluoro butane-1,2-glycol;
(b) make 1,1,1-trifluoro butane-1, the reaction of 2-glycol and a kind of sulfonic acid halide, generate corresponding 1,1,1-trifluoro butane-2,4-sulphonate;
(c) make 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1,1-trifluoro butane; With
(d) make 2,4-two bromo-1,1,1-trifluoro butane and a kind of defluorinate bromide react in liquid reaction medium.
5. one kind prepares 2,4-two bromo-1,1, and the method for 1-trifluoro butane, this method comprises makes 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1, the step of 1-trifluoro butane.
6. preparation 2 according to claim 5,4-two bromo-1,1, the method for 1-trifluoro butane, this method comprises the following steps:
(a) make 1,1,1-trifluoro butane-1, the reaction of 2-glycol and a kind of sulfonic acid halide, generate corresponding 1,1,1-trifluoro butane-2,4-sulphonate; With
(b) make 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1,1-trifluoro butane.
7. preparation 2 according to claim 5,4-two bromo-1,1, the method for 1-trifluoro butane, this method comprises the following steps:
(a) make the reaction of trifluoromethyl-ethanoyl ethyl acetate and borohydride, generate 1,1,1-trifluoro butane-1,2-glycol;
(b) make 1,1,1-trifluoro butane-1, the reaction of 2-glycol and a kind of sulfonic acid halide, generate corresponding 1,1,1-trifluoro butane-2,4-sulphonate; With
(c) make 1,1,1-trifluoro butane-2,4-sulphonate and the reaction of a kind of bromide source generate 2,4-two bromo-1,1,1-trifluoro butane.
8. according to the process of claim 1 wherein that this defluorinate bromide is selected from metallic zinc, aluminium and magnesium.
CN96197873A 1995-09-06 1996-08-23 Process for preparing 4-bromo-1,1-difluorbut-1-ene and 2,4-dibromo-1,1,1-trifluorobutane Pending CN1200717A (en)

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GB9518111.1 1995-09-06

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HUP9802542A2 (en) 1999-02-01
ZA967262B (en) 1997-03-06
JPH11512110A (en) 1999-10-19
WO1997009292A1 (en) 1997-03-13
KR19990044419A (en) 1999-06-25
GB9518111D0 (en) 1995-11-08
HUP9802542A3 (en) 1999-03-29

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