Process for preparing 3,3,3-trifluoroprop-1-ene
The present application provides a process of preparing 3,3,3-trifluoroprop-1-ene, comprising reacting 3-chloro-1,1,1-trifluoropropane with a base in an aqueous solvent component in the absence of a phase transfer catalyst.
1. A process of preparing a mixture of 3,3,3-trifluoropropene (HFO-1243zf), the process comprising reacting 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) with a base in a liquid phase comprising an aqueous solvent in the presence of an amine and in the absence of a phase transfer catalyst.
2. The process of claim 1 , wherein the amine is selected from the group consisting of a primary unsubstituted alkyl amine of the formula RNH 2 wherein R is a C 1 -C 16 unsubstituted alkyl group, a secondary unsubstituted alkyl amine of the formula R1R2NH wherein each R1 and R2 is independently a C 1 -C 6 unsubstituted alkyl group, and a tertiary unsubstituted alkyl amine of the formula R1R2R3N wherein each R1, R2 and R3 is independently a C 1 -C 6 unsubstituted alkyl group.
3. The process of claim 2 , wherein the amine is:
(i) a primary unsubstituted alkyl amine selected from the group consisting of methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, amylamine, isoamylamine, tert-amylamine, hexylamine, and mixtures thereof; or
(ii) a secondary unsubstituted alkyl amine selected from the group consisting of dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-sec-butylamine, diamylamine, dihexylamine, and mixtures thereof; or
(iii) a tertiary unsubstituted alkyl amine selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, and mixtures thereof.
4. The process of claim 1 , wherein the amine is selected from the group consisting of:
(i) methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, tripropylamine, butylamine, sec-butylamine, tert-butylamine, dibutylamine, tributylamine, di-sec-butylamine, amylamine, isoamylamine, tert-amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, 1,1,3,3-tetramethylbutylamine), N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, and mixtures thereof; or
(ii) ethanolamine (H2NCH2CH2OH), diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2), 2-(methylamino)ethanol (CH3NHCH2CH2OH), 2-(ethylamino)ethanol (CH3CH2NHCH2CH2OH), 2-(propylamino)ethanol (CH3CH2CH2NHCH2CH2OH), 2-(isopropylamino)ethanol ((CH3)2CHNHCH2CH2OH), 2-(butylamino)ethanol (CH3(CH2)3NHCH2CH2OH), 2-(tert-butylamino)ethanol ((CH3)3CNHCH2CH2OH), triisopropanolamine ([CH3CH(OH)CH2]3N), N,N-dimethylethanolamine (HOCH2CH2N(CH3)2), 1-dimethylamino-2-propanol ((CH3)2NCH2CH(OH)CH3), 3-dimethylamino-1-propanol ((CH3)2N(CH2)3OH), 2-amino-2-methyl-1-propanol ((CH3)2C(NH2)CH2OH), and mixtures thereof; or
(iii) ethanolamine (H2NCH2CH2OH), tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2), 2-(methylamino)ethanol (CH3NHCH2CH2OH), 2-(ethylamino)ethanol (CH3CH2NHCH2CH2OH), 2-(propylamino)ethanol (CH3CH2CH2NHCH2CH2OH), 2-(isopropylamino)ethanol ((CH3)2CHNHCH2CH2OH), 2-(butylamino)ethanol (CH3(CH2)3NHCH2CH2OH), 2-(tert-butylamino)ethanol ((CH3)3CNHCH2CH2OH), N,N-dimethylethanolamine (HOCH2CH2N(CH3)2), 1-dimethylamino-2-propanol ((CH3)2NCH2CH(OH)CH3), 3-dimethylamino-1-propanol ((CH3)2N(CH2)30H), 2-amino-2-methyl-1-propanol ((CH3)2C(NH2)CH2OH), and mixtures thereof; or
(iv) 3-(dimethylamino)propylamine OCH3)2N(CH2)3NH2), 3-(diethylamino)propylamine ((C2H5)2N(CH2)3NH2), and mixtures thereof; or
(v) ethylene diamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-pentanediamine, spermidine (N-(3-aminopropyl)butane-1,4-diamine), spermine (N,N′-bis(3-aminopropyl)butane-1,4-diamine), diethylenetriamine, triethylenetetramine, and mixtures thereof; or
(vi) pyrrolidine, pyrroline (including 1-pyrroline, 2-pyrroline and 3-pyrroline), piperidine, piperazine, morpholine, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, pyridine, bipyridine (including 2,2′-bipyridine, 4,4′-bipyridine, 2,3′-bipyridine, and 3,4′-bipyridine, etc.), and mixtures thereof; or
(vii) aniline, o-toluidine, m-toluidine, p-toluidine, xylidine, 2,4,6-trimethylaniline, o-anisidine, m-anisidine, p-anisidine, N-methylaniline, N,N-dimethylaniline, N-ethylaniline, N,N-diethylaniline, and mixtures thereof.
5. The process of claim 1 , wherein the amine is selected from the group consisting of aromatic amines, heterocyclic amines, hydrazine and its derivatives, and mixtures thereof.
6. The process of claim 1 , wherein the amine is a trialkyl amine or dialkyl amine.
7. The process of claim 1 , wherein a mole ratio of amine to 3-chloro-1,1,1-trifluoropropane ranges from about 0.02 to about 3.
8. The process of claim 1 , wherein a mole ratio of amine to base ranges from about 0.05 to about 3.
9. The process of claim 1 , wherein the aqueous solvent comprises up to 40 weight percent of an organic solvent.
10. The process of claim 9 , wherein the organic solvent is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, and butanol.
11. The process of claim 1 , wherein the base is a metal hydroxide base, a metal carbonate base, a metal phosphate base, or a metal fluoride base.
12. The process of claim 1 , wherein the base is selected from the group consisting of NaOH, KOH, LiOH, CsOH, Ca(OH)2, Zn(OH)2, Na2CO3, K2CO3, K3PO4, Na3PO4, KF, and CsF.