2-oxo-1,3-dioxolane-4-acyl halides, their preparation and use

Abstract

The present invention suggests 2-oxo-1,3-dioxolane-4-acyl halides of formula (I), ##STR00001##
wherein X is selected from F, Cl, Br, I and mixtures thereof, preferably Cl, processes for the preparation of said 2-oxo-1,3-dioxolane-4-acyl halides, the use of said 2-oxo-1,3-dioxolane-4-acyl halides for the preparation of 2-oxo-1,3-dioxolane-4-carboxylic esters of formula (II), ##STR00002##
the use of said 2-oxo-1,3-dioxolane-4-acyl halides for the preparation of 2-oxo-1,3-dioxolane-4-carboxamides of formula (III), ##STR00003##
and also the use of said 2-oxo-1,3-dioxolane-4-acyl halides as agents for the blocking of amines.

Claims

1. 2-Oxo-1,3-dioxolane-4-acyl halide of formula (I), ##STR00029## wherein X is selected from F, Cl, Br, I and mixtures thereof.

2. The 2-Oxo-1,3-dioxolane-4-acyl halide according to claim 1, wherein X is Cl.

3. A process for the preparation of the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1, wherein 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (X) ##STR00030## is reacted with an halogenation agent.

4. The process according to claim 3, wherein the halogenation agent is SOCl.sub.2.

5. The process according to claim 4, wherein the reaction is carried out without a solvent at an elevated temperature.

6. The process according to claim 5, wherein the halogenation is carried out at about 60 C. in the presence of dimethylformamide as a catalyst.

7. A process comprising reacting the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 with an alcohol R.sub.1OH for the preparation of a 2-oxo-1,3-dioxolane-4-carboxylic ester of formula (II), ##STR00031## wherein R.sub.1 is selected from straight-chain C.sub.1-12-alkyl groups, branched or cyclic C.sub.3-12-alkyl groups, C.sub.6-10-aryl groups, C.sub.6-12-aralkyl groups and C.sub.6-12-alkaryl groups.

8. A process comprising reacting the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 with a multifunctional polyol comprising R.sub.1 for the preparation of a 2-oxo-1,3-dioxolane-4-carboxylic ester of formula (II), ##STR00032## wherein R.sub.1 is a radical having a valency of 2 to 6, which is substituted with 1 to 5 further 2-oxo-1,3-dioxolane-4-carboxylic ester groups.

9. A process comprising reacting the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 with an amine NH.sub.2R.sub.1 for the preparation of a 2-oxo-1,3-dioxolane-4-carboxamide of formula (III), ##STR00033## wherein R.sub.1 and R.sub.2, in each case independently of one another, are selected from H, straight-chain C.sub.1-12-alkyl groups, branched or cyclic C.sub.3-12-alkyl groups, C.sub.6-10-aryl groups, C.sub.6-12-aralkyl groups and C.sub.6-12-alkaryl groups or, together with the N atom to which they are bonded, form a 5- to 8-membered ring.

10. A process comprising reacting the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 with a multifunctional amine comprising R.sub.2 for the preparation of a 2-oxo-1,3-dioxolane-4-carboxamide of formula (III), ##STR00034## wherein R.sub.1 is selected from H, straight-chain C.sub.1-12-alkyl groups, branched or cyclic C.sub.3-12-alkyl groups, C.sub.6-10-aryl groups, C.sub.6-12-aralkyl groups, C.sub.6-12-alkaryl groups, or a polypeptide residue, and R.sub.2 is a radical having a valency of 2 to 6, which is substituted with 1 to 5 further 2-oxo-1,3-dioxolane-4-carboxamide groups.

11. A process comprising blocking an amine by reaction with the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1.

Description

EXAMPLES

Example 1 (Reference): Acidic Hydrolysis of 4-methoxycarbonyl-2-oxo-1,3-dioxolane

(1) ##STR00021##

(2) 73 g (0.5 mol) of 4-methoxycarbonyl-2-oxo-1,3-dioxolane (EP 2397474 A1) was heated under reflux for 3 hours with 11 g (0.55 mol) of water and 48 g (0.8 mol) of acetic acid. The mixture was then added to cyclohexane, the separated-off oil was carefully freed from all volatile constituents and the residue was ground with methylene chloride until a colourless crystalline precipitate had formed. The precipitate was washed with diethyl ether and dried in vacuo. This gave 2-oxo-1,3-dioxolane-4-carboxylic acid.

(3) m.p.: 119-121 C. .sup.1H-NMR (CDCl.sub.3/DMSO-d6 (1/0.1 [mol/mol])): 9.486 (broad, s; 1H); 5.012 (dd; 1H); 4.637 (t; 1H); 4.506 (dd; 1H). .sup.13C-NMR (CDCl.sub.3/DMSO-d6 (1/0.1 [mol/mol])): 168.425 (CO acid); 153.348 (CO cyclocarbonate); 72.247 (CHCOOH); 66.988 (CH.sub.2CHCOOH). IR (v [cm.sup.1]): 2977 bs (OH acid), 2751 bw, 2658 bw, 2621 bw, 2538 bw, 2407 bw, 1785 bm (CO cyclocarbonate), 1793 bs (CO acid), 1546 w, 1481 w, 1431 w, 1399 s, 1345 w, 1325 w, 128 m, 1196 s, 1087 s, 1074 s, 1039 m, 928 w, 832 s, 769 s, 724 m, 699 s, 650 m, 633 s, 525 s.

Example 2 (Reference): N-Oxide-Mediated Oxidation of Glycerol Carbonate

(4) ##STR00022##

(5) (Procedure analogous to JOC 2003; 68; pages 4999 ff.) 118.1 g (1 mol) of glycerol carbonate, 168 g (2 mol) of sodium hydrogencarbonate, 232 g (1 mol) of trichloroisocyanuric acid, 18 g (1 mol) of water, 1.5 g (0.01 mol) of TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) and 5 g (0.05 mol) of NaBr were introduced in 1.5 l of acetone at 0 C. with stirring. The mixture was left to warm to room temperature and stirred for a further 12 hours, after which it was filtered off. The filtrate was concentrated by evaporation. The resulting oil was heated at reflux with chloroform. This gave 2-oxo-1,3-dioxolane-4-carboxylic acid in 97% yield.

Example 3: Synthesis of 2-oxo-1,3-dioxolane-4-acyl chloride

(6) ##STR00023##

(7) In a dry schlenk tube under an atmosphere of dry N2, 2.5 g (0.019 mol) of 2-oxo-1,3-dioxolane-4-carboxylic acid, 2.5 g (0.021 mol) of freshly distilled thionyl chloride and 0.115 ml of dimethylformamide were heated to 50 C. until the formation of a clear solution. The reaction mixture was heated to 60 C. for 2 h. After DMF and the excess of thionyl chlorid were removed in vacuo, 2-oxo-1,3-dioxolane-4-acyl chloride was obtained as a colorless liquid in quantitative yield.

(8) .sup.1H-NMR (400 MHz, DMSO-d6): =5.27 (dd, 1H, CH.sub.2), 4.71 (t, 1H, CH), 4.52 (dd, 1H, CH.sub.2) ppm; .sup.13C-NMR (100 MHz, DMSO-d6): =169.5 (CO), 154.7 (OC(O)O), 72.9 (CH), 67.7 (CH.sub.2) ppm; IR (v, cm.sup.1): 2976 (bw, COOH), 1802 (s, cyclocarbonate), 1668 (w), 1529 (w), 1480 (w), 1385 (m), 1310 (w), 1210 (w), 1147 (s), 1104 (m), 1060 (s), 921 (s), 882 (s), 760 (s), 699 (s), 640 (w), 560 (m), 526 (m); GC-MS (EtAc, RT: 8.73 min): m/z=86.99 [Cyclocarbonate].sup.+, 62.93 [CClO].sup.+.

Example 4: Reactivity of 2-oxo-1,3-dioxolane acyl chloride

(9) ##STR00024##

(10) In a dry schlenk tube under an atmosphere of dry N2, to 2.86 g (0.019 mol) of 2-oxo-1,3-dioxolane acyl chloride was carefully added 0.73 g (0.023 mol) of methanol. During the exothermic reaction the evolution of HCl-gas was observed. The reaction was cooled to RT using a cold water bath, the excess of MeOH was removed in vacuo and 2-oxo-1,3-dioxolane carboxylic acid methyl ester was obtained in quantitative yield. The analytical data agree with known data of 2-oxo-1,3-dioxolane carboxylic acid methyl ether.

Example 5: Reactivity of 2-oxo-1,3-dioxolane acyl chloride

(11) ##STR00025##

(12) In a dry schlenk flask under an atmosphere of dry N2, 2.86 g (0.019 mol) 2-oxo-1,3-dioxolane carbonyl chloride was diluted with 20 ml abs. THF and cooled to 0-4 C. using an ice bath. In a dropping funnel 0.019 mol n-butylamine and 2.31 g (0.019 mol) triethylamine were mixed and diluted with 10 ml abs. THF. This mixture was carefully added to the acid chloride at 0-4 C. Immediately a white precipitate of Et.sub.3NCl formed. The reaction mixture was stirred at 0-4 C. for 1 h and additional 12 h at RT. The precipitate was filtered off and the solvent was removed in vacuo. N-n-butyl-2-oxo-1,3-dioxolane-4-carboxamide was obtained as a brownish oil in 96% yield. Analytic data agree with known data of N-n-butyl-2-oxo-1,3-dioxolane-4-carboxamide prepared from 2-oxo-1,3-dioxolane carboxylic acid and n-butylisocyanate.

Example 6: Reactivity of 2-oxo-1,3-dioxolane acyl chloride

(13) ##STR00026##

(14) In a dry schlenk flask under an atmosphere of dry N2, 2.86 g (0.019 mol) 2-oxo-1,3-dioxolane-4-carbonyl chloride was diluted with 10 ml abs. THF and cooled to 0-4 C. using an ice bath. In a dropping funnel 1.88 g cyclohexylamine (0.019 mol) and 2.31 g (0.019 mol) triethylamine were mixed and diluted with 20 ml abs. THF. This mixture was carefully added to the acid chloride at 0-4 C. Immediately a white precipitate of Et.sub.3NCl formed. The reaction mixture was stirred at 0-4 C. for 1 h and additional 12 h at RT. The precipitate was filtered off and the solvent was removed in vacuo. N-cyclohexyl-2-oxo-1,3-dioxolane-4-carboxamide was obtained as a beige powder in 94% yield. The analytical data agree with known data of N-cyclohexyl-2-oxo-1,3-dioxolane-4-carboxamide prepared from 2-oxo-1,3-dioxolane-4-carboxylic acid and cyclohexyl-isocyanate.

Example 7: Formation and Curing of Multifunctional Binders from 2-oxo-1,3-dioxolane-4-acyl chloride

(15) ##STR00027##

(16) In a dry schlenk flask under an atmosphere of dry N2, 30.10 g (0.2 mol) 2-oxo-1,3-dioxolane carbonyl chloride (CYCA-chloride) was diluted with 70 ml abs. THF and cooled to 0-4 C. using an ice bath. In a dropping funnel 29.33 g polyetheramine T 403 (BASF SE, 0.2 mol) and 24.29 g (0.24 mol) triethylamine were mixed and diluted with 40 ml abs. THF. This mixture was carefully added to the acid chloride at 0-4 C. Immediately a white precipitate of Et.sub.3NCl formed. The reaction mixture was stirred at 0-4 C. for 1 h and additional 12 h at RT. The precipitate was filtered off and the solvent was removed in vacuo. The trifunctional product was obtained as a red-brown oil in almost quantitative yield.

(17) IR (v, cm.sup.1): 3311 (bw), 3082 (w), 2972 (w), 2932 (w), 2874 (w), 1811 (s, cyclocarbonate), 1666 (s), 1541 (m), 1456 (m), 1385 (m), 1378 (m), 1255 (w), 1153 (s), 1080 (s), 1060 (s), 922 (w), 840 (w), 768 (m), 730 (w), 661 (w).

(18) The procedure was analogously carried out with Polyetheramine T 5000 (BASF SE) or Jeffamine T 3000 (Huntsman). The properties are summarized in Table 1 hereinbelow:

(19) TABLE-US-00001 TABLE 1 Amount Amount [g] [mol] Properties CYCA-chloride 30.10 0.2 T 403 29.33 0.2 Red-brown viscous liquid, 2.650.000 mPas, Meq = 261 g/mol T 3000 200.00 0.2 Red-brown liquid, 10.500 mPas, Meq = 1115 g/mol T 5000 333.33 0.2 Red-brow liquid, 6.000 mPas, Meq = 1800 g/mol NEt.sub.3 24.29 0.24

(20) The resulting products can be cured with different amines to give stable hydroxypoly-urethane films. The results are summarized in Table 2 hereinbelow:

(21) TABLE-US-00002 TABLE 2 Binder Amine T403-CYCA T3000-CYCA T5000-CYCA Lupasol FG Cured, tack-free, Cured, tack-free, (BASF SE) .sub.M = 0.99 .sub.M = 0.44 N/mm.sup.2, N/mm.sup.2, .sub.M = 35% .sub.M = 125% IPDA Cured, tack-free, Not completely brittle cured, tacky T 403 Cured, tack-free, Cured, elastic Not completely (Huntsman) .sub.M = 0.86 cured, tacky N/mm.sup.2, .sub.M = 78%

(22) Cyclocarbonate-functional binders can also be prepared from 2-oxo-1,3-dioxolane carbonyl chloride using triols (such as Lupranol 1301 or 2048) instead of triamines.

Example 8: Formation and Curing of Multifunctional Binders from 2-oxo-1,3-dioxolane-4-acyl chloride

(23) Cyclocarbonate-functional binders were also prepared from 2-oxo-1,3-dioxolane-4-carbonyl chloride using triols (such as Lupranol 1301 or 2048, BASF SE) instead of triamines:

(24) ##STR00028##

(25) In a dry schlenk flask under an atmosphere of dry N2, 10.00 g (0.07 mol) 2-oxo-1,3-dioxolane-4-acyl chloride were diluted with 200 ml abs. THF and cooled to 0-4 C. using an ice bath. In a dropping funnel 88.18 g Lupranol 2048 (BASF SE, 0.07 mol) and 8.00 g (0.08 mol) triethylamine were mixed and diluted with 50 ml abs. THF. This mixture was carefully added to the acid chloride at 0-4 C. Immediately a white precipitate of Et.sub.3NCl formed. The reaction mixture was stirred at 0-4 C. for 1 h and additional 12 h at RT. The precipitate was filtered off and the solvent was removed in vacuo. The trifunctional product was obtained as a red-brown oil in almost quantitative yield. (Lupranol 1301 can be used analogously.)

(26) IR (v, cm.sup.1): 2865 (s), 1821 (s, cyclocarbonate), 1752 (m), 1455 (m), 1373 (m), 1349 (m), 1296 (m), 1248 (m), 1090 (vs), 1060 (s), 949 (m), 846 (w), 768 (w).

(27) The resulting products were subsequently cured with different amines to give hydroxy-polyurethane films. The results are summarized in Table 3 hereinbelow:

(28) TABLE-US-00003 TABLE 3 Binder Amine 2048-CYCA (M.sub.eq = 255 g/mol) Lupasol FG Not completely cured (BASF SE) IPDA Not completely cured T 403 Not completely cured (Huntsman)

(29) Due to the lower stability of the ester groups in comparison to the amide groups in the triamine-based products, a poorer curing behavior is observed and less stable films are obtained.