CZ306988B6 - The method of preparing lactyl lactate hydrocarbyl esters from lactides - Google Patents

Abstract

The present invention provides a process for preparing hydrocarbyl esters lactate lactate lactate, where the lactide is contacted with hydrocarbyl alcohol and hydrogen halide to form lactate lact carboxylate esters.

Description

Technical field

The invention relates to a process for the preparation of biodegradable lactyl lactate esters.

BACKGROUND OF THE INVENTION

Lactides are cyclic diesters of lactic acid (2-hydroxypropanoic acid) from which it is produced by dehydrating its two molecules in the presence of a catalyst. There are three stereoisomers according to CAS 4511-42-6 ((S, S) -lactide), 25038-75-9 ((RR) -lactide)), 13076-19-2 ((R, S) -lactide = meso lactide), 26680-10-4 (mixture of three isomers), 95-96-5 (mixture of three isomers). Presently, the main uses of lactides are probably their polymerization to polylactides and other copolymers [R. Auras; L.-T. Lim; S.E.M Selke; H. Tsuji (2010). Poly (lactic acid): Synthesis, Structures, Properties, Processing, and Applications. Wiley. ISBN 978-0-470-29366-9]. These biocompatible and biodegradable oligo- / polymers currently appear to be a good substitute for synthetic (fossil) oligo- / polymers and, in addition, can be produced in the long term from natural sources (biomass, vegetable oil, corn, cotton, proteins, etc.) with a wide range of uses in medicine - such as prosthetics, degradable stitches or drug carriers - and in the polymer and packaging industry.

Ring-opening polymerization of lactides is typically catalyzed / initiated by transition and non-transition metal complexes such as Zn, Al, Sn, or by catalyst systems in which these compounds are present. A disadvantage of polymerizations utilizing the catalytic action of metal complexes is the possibility of introducing the organometallic contaminants into the prepared oligo- / polyester, thereby reducing its biogenic compatibility.

Lactic acid can also be used to prepare oligomers, the so-called lactylates (Scheme 1), which are most often produced by esterifying them with the corresponding acyl chlorides of higher fatty acids. Lactlates are unique in that they contain both polar and non-polar functional groups in their structure, thus interacting with hydrophilic and lipophilic substances, which, together with their low toxicity, allows their application in the food and cosmetics industry. They are added as emulsifiers to the dough products, as they facilitate its processing, rising, counteracting the premature aging of baked goods (peeling) and antimicrobial. They play an irreplaceable role in a number of cosmetic products (creams, conditioners, face masks, etc.) and their sodium salts have proven antimicrobial effects and are highly active in certain families of Gram positive bacteria (Clostridium perfringens) and are therefore an additive of highly selective antibiotics. In the human body, lactylates are degraded / hydrolyzed to lactic acid and the corresponding fatty acid and subsequently to simpler, also exclusively biogenic metabolites.

Industrial polymers are biodegraded with min. 92% efficiency, thus meeting the requirements for biodegradable materials.

HIM

Me

O

About me

STEED

AND

RO

Me

O

OH or

O

About me

Scheme 1: General structure of lactylate lactate (A) and lactylates (B right), respectively. its salts (B left)

Selectively prepared lactyl lactates are a natural replacement for lactylates. Lactic acid, which contains two reactive functional groups - hydroxyl and carboxylic acid, can serve as a precursor for the preparation of lactyl lactates. The carboxyl group can be suitably activated and subsequently reacted with other substrates (alcohols, etc.) as well as with the hydroxyl group of lactic acid to form oligo / polyesters or mixtures thereof. One way to prevent this process, and to control the entire lactate synthesis, is to use a process using the protection of one of the reactive groups, which is unfortunately associated with high experimental demands [K. Phomphrai, S. Dust, P. Phonjanthuek, M. Pohmakotr, Dalton Trans., 2008, 3048]. For this reason, it is preferable to use a ring opening strategy based on the cyclic diester of lactic acid (lactide) for the synthesis of lactyl lactates. This approach is discussed in U.S. Pat. Nos. 2,371,281, 5,688,850, wherein the products synthesized are hardly separable mixtures of individual oligomers / esters, and in addition the entire synthesis proceeds under drastic conditions using concentrated sulfuric acid or benzenesulfonic acid as the catalyst. WO 2008/006076 mentions the same approach, in which sulfuric acid, in particular, is used as the acid catalyst, and the reaction proceeds at milder temperatures but at several times longer reaction times (1-3 days) to achieve complete conversion. 1, a mixture of esters and oligomers is formed.

An alternative option is the selective esterification of lactides initiated, for example, by calcium bisalkoxides generated in situ in a reaction mixture containing lactide and Aso-propanol, to produce isopropyl lactyl lactates [Z. Zhong, S. Schneiderbauer, P.J. Dijkstra, M. Westerhausen, J. Feijen, J. Polym. Environ., 2001, 9, 31], Other complexes useful for the chemoselective alcoholysis of the lactide cycle are amides or amino-phenolates based on metals I and II. groups [A. Grala, J. Ejfler, L.B. Jerzykiewicz, P. Saturday, Dalton Trans., 2011, 40, 4042. D. Bykowski, A. Grala, P. Saturday, Tetrahedron Flying. 2014, 55, 5286. H. Kampova, E. Riemlova, J. Klikarova, V. Pejchal, J. Mema, P. Vlasak, P. Svec, Z. Ruzickova, A. Ruzicka, J. Organomet. Chem., 2014, 778, 35. R. Olejnik, M. Bilek, Z. Ruzickova, Z. Hostalek, J. Mema, A. Ruzicka, J. Organomet. Chem., 2015, 794,237]. Last but not least, the lactide ring can be opened by enzymes (Novozym 435). Y. Jeonn S.-J. Ko, K. Won, H.-Y. Kang, B.T. Kim, Y.L. Lee, H. Lee, Tetrahedron Leti., 2006, 47, 6517], the processing of products being discussed in WO2013 / 011298.

It is an object of the present invention to provide a simple, inexpensive, rapid and selective method for preparing alkyl and aryl lactyl lactates from lactides.

SUMMARY OF THE INVENTION

The present invention solves the present object by providing a process for the preparation of lactyl lactate ester from lactide, wherein the formation of lactyl lactates from lactide is initiated by volatile hydrogen halides in the corresponding alcohol, which is then the source of the hydrocarbyl ester group.

It is therefore an object of the present invention to provide a process for preparing a hydrocarbyl ester of lactyl lactates from a lactide, wherein the lactide is contacted with the hydrocarbyl alcohol and hydrogen halide.

The hydrocarbyl alcohol is selected from polyethylene glycols having a molar mass of up to 20,000 g / mol, preferably in the range of 300 to 10,000 g / mol, and aliphatic, alicyclic or aromatic alcohols having 1 to 30 carbon atoms, more preferably 1 to 18 carbon atoms, and 1 to 5 hydroxyl groups, more preferably 1 to 3 hydroxyl groups, wherein optionally one or more, more preferably 1 to 5, -CH 2 - groups may be replaced by -O-. The hydrocarbyl chain is linear or branched and may optionally contain at least one double and / or triple bond. The hydrocarbyl alcohols of the present invention are preferably polyethylene glycols, glycols, glycerol, monohydroxy alcohols. Aromatic alcohols include phenols.

Preferably, the hydrocarbyl alcohol is selected from the group consisting of methanol, propan-1-ol, butan-1-ol, propan-2-ol (2-propanol), 2-methyl propan-2-ol (tert-butanol), 2-methylpropan-2-ol. -ethyl-hexan-1-ol,

-2EN 306988 B6 phenol, cyclohexanol, trimethylolpropane oxetane (TMPO), trimethylolpropane diallyl ether (TMPDE), butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10 Diol, octadecan-1-ol, cis-9-octadecen-1-ol, hexadecan-1-ol.

The reaction is preferably carried out in an aromatic solvent, in particular toluene, benzene, xylene. L-lactide, D-lactide, or a mixture thereof, for example a racemate, can be used for the reaction.

The hydrogen halide is selected from the group consisting of HCl, HBr, HI.

The esterification reaction is preferably carried out at a temperature in the range of 35 to 90 ° C for 15 to 90 minutes.

Advantages of the process of the present invention are that precursors of common commercial purity can be used for esterification without further drying and distillation, all volatile components are easily removed after the reaction by distillation under reduced pressure (typically 40 ° C / 1 mbar, i.e. 14 Pa). The reaction in quantitative yields and selectively produces lactyl lactates, which need not be further purified by distillation.

The reactions can also be carried out on an industrial scale. The finished products do not contain residues of biologically unacceptable metals, so they can be used directly for medical and food applications.

Preferably, the reaction mixture contains an excess of lactide, hydrocarbyl alcohol in excess of the lactide, and 0.04 to 0.1, preferably 0.06 to 0.08, molar equivalent of hydrogen halide relative to the lactide. After completion of the reaction, the mixture is worked up by extraction or evaporation of all volatiles, the residue is subsequently washed with hydrocarbon and dried in vacuo.

DETAILED DESCRIPTION OF THE INVENTION

Me OO Me ' ^Λ Τ °' 5 ^Λο - (CH ₂ ) '- o

O Me Me O n = 4, butane-1,4-diyl

5, pentane-1,5-diyl

6, hexane-1,6-diyl 10, decane-1,10-diyl + HO- (CH _{2) n} -OH

HX (X = Cl, 8r and I) toluene

Me

- (CH ₂ ) ₃ -Me / (CH ₂ ) ₁₅ -Me '- *

- (CH ₂ ), _T- Me

Me

Me

-H0

- (H ₂ C) e -HC = HC- (CH ₂ ) ₇ -Me

Me

Scheme 2: Summary of the reactions shown in the Examples

Example 1. Preparation of (2S) -1-methoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and methanol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of L-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of methanol (0.12 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. They were then evaporated under reduced pressure

-3GB 306988 B6 All volatile components. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 S) -1-methoxy-1-oxopropan-2-yl (2 S) -2-hydroxypropanoate was 1.32 g (7.45 mmol, 98%). Elemental analysis for C 7 H 12 O 5 (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.6; H,

6.6. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.02 (q, J _H -h = 7.1 Hz, 1H, OC // (Me) COO), 4.30 (q, J _{H H} = 7.1 Hz, 1H, HOC / 7 (Me)), 3.80 (br s, 1H, HO), 3.29 (s, 3H, COOC / 3), 1.45 (d, J _H -H = 7.0 Hz, 3H, OCH (CTF ₃₎ COO), 1.19 (d, J _H -H = 7.2 Hz, 3H, HOCH _(7/3)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.5 (COOMe), 171.3 (C (Me) COO), 69.6 (OC (Me) COOMe), 67.3 (HOC) (Me)), 52.2 (COOCH ₃ ), 20.8 (OC (CH ₃ ) COO), 17.0 (HOC (CH ₃ ) COO). GC-MS: m / z = 176.07 for [lactyl-lactate-Me] ⁺ .

Example 2. Preparation of (2S) -1-methoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and methanol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 mL of methanol (0.12 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-methoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.32 g (7.44 mmol, 98%). Elemental analysis for C ₇ H ₁₂ O ₅ (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.5; H,

6.7. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.02 (q, J _H -h = 7.1 Hz, 1H, OC // (Me) COO), 4.30 (q, J _{H H} = 7.1 Hz, 1H, HOC (t) (Me)), 3.80 (br s, 1H, HO), 3.29 (s, 3H, COOC / 7.1), 1.45 (d, J _H -H = 7.0 Hz, 3H, OCH (C77 ₃₎ COO), 1.19 (d, J _H -H = 7.2 Hz, 3H, HOCH (Gtfj)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.5 (COOMe), 171.3 (C (Me) COO), 69.6 (OC (Me) COOMe), 67.3 ( HOC (Me)), 52.2 (COOCH ₃ ), 20.8 (OC (CH ₃ ) COO), 17.0 (HOC (CH ₃ ) COO). GC-MS: m / z = 176.07 for [lactyl-lactate-Me] ⁺ .

Example 3. Preparation of (2S) -1-methoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and methanol initiated by H1

A 25 mL round bottom flask was charged with 1.1 g of β-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of methanol (0.12 mol) + 0.05 ml of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -methoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.33 g (7.55 mmol, 99%). Elemental analysis for C ₇ H ₁₂ O ₅ (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.4; H,

6.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.02 (q, J _H -h = 7.1 Hz, 1H, OC // (Me) COO), 4.30 (q, J _{H H} = 7.1 Hz, 1H, HOC 77 (Me)), 3.80 (br s, 1H, HO), 3.29 (s, 3H, COOCH ₃ ), 1.45 (d, J _H-H = 7.0 Hz, 3H, OCH (C 7 _H ) COO), 1.19 (d, J _H = _H = 7.2 Hz, 3 H, HOCH (C 6 H)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.5 (COOMe), 171.3 (C (Me) COO), 69.6 (OC (Me) COOMe), 67.3 ( HOC (Me)), 52.2 (COOCH ₃ ), 20.8 (OC (CH ₃ ) COO), 17.0 (HOC (CH ₃ ) COO). GC-MS: m / z = 176.07 for [lactyl-lactate-Me] ⁺ .

-4GB 306988 B6

Example 4. Preparation of (2R) -1-methoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and methanol initiated by HCl

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of methanol (0.12 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2R) -1-methoxy-1-oxopropan-2-yl (2A) -2-hydroxypropanoate was 1.33 g (7.54 mmol, 99%). Elemental analysis for C 7 H 12 O 5 (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.6; H, 6.9. * H NMR (500 MHz, C ₆ D _6, 298K) δ 5.01 (q, J _H-H = 7.0 Hz, 1H, oc7 / (Me) COO)

4.28 (q, δι η = 7.0 Hz, 1H, HOC (Me)), 3.82 (br s, 1H, HO), 3.27 (s, 3H, COOC / Tj), 1 43 (d, J _{H- H} = 7.0 Hz, 3H, OCH (CTfy) COO), 1.21 (d, J _H-H = 7.2 Hz, 3H, HOCH (Ctf ₃ )) · ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.3 (COOMe), 171.1 (C (Me) COO), 69.9 (OC (Me) COOMe), 67.1 (HOC (Me) )),

52.4 (COOCH 3), 20.6 (OC (CH ₃ ) COO), 15.9 (HOC (CH ₃ ) COO). GC-MS: m / z = 176.07 for [lactyl-lactate-Me] ⁺ .

Example 5. Preparation of (2R) -1-methoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and methanol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of methanol (0.12 mol) + 0.05 ml of HBr (conc. 48%>, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 R) -1-methoxy-1-oxopropan-2-yl (2A) -2-hydroxypropanoate was 1.33 g (7.55 mmol, 99%>). Elemental analysis for C 7 H 12 O 5 (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.7; H, 6.6. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.01 (q, J _H -h = 7.0 Hz, 1H, OCtf (Me) COO),

4.28 (q, J _{H- H} = 7.0 Hz, 1H, HOCD (Me)), 3.82 (br s, 1H, HO), 3.27 (s, 3H, COOC / phy), 1 43 (d, J _{H- H} = 7.0 Hz, 3H, OCH (CH3) COO), 1.21 (d, J _H-H = 7.2 Hz, 3H, HOCH (Ct H)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.3 (COOMe), 171.1 (C (Me) COO), 69.9 (OC (Me) COOMe), 67.1 (HOC) (Me)),

52.4 (COOCH ₃ ), 20.6 (OC (CH ₃ ) COO), 15.9 (HOC (CH ₃ ) COO). GC-MS: m / z = 176.07 for [lactyl-lactate-Me] ⁺ .

Example 6. Preparation of (2R) -1-methoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and methanol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of methanol (0.12 mol) + 0.05 mL of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2A) -1-methoxy-1-oxopropan-2-yl (2A) -2-hydroxypropanoate was 1.32 g (7.49 mmol, 98%). Elemental analysis for C ₇ H ₂ O ₅ (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.9; H, 6.9. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.01 (q, J / _H = 7.0 Hz, 1H, OCtf (Me) COO),

4.28 (q, J _H ^< 11 ^> = ⁷ > ^{Hz &gt}; ^1H , HOCtf (Me)), 3.82 (br s, 1H, HO), 3.27 (s, 3H, COOCH3), 1.43 ( d,

-5H 306988 B6 _H = 7.0 Hz, 3H, OCH (Ct H ₅ ) COO), 1.21 (d, J _H -h = 7.2 Hz, 3 H, HOCH (C 77 ₃ )). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.3 (COOMe), 171.1 (C (Me) COO), 69.9 (OC (Me) COOMe), 67.1 (HOC) (Me)),

52.4 (COOCHj), 20.6 (OC (CH ₃₎ COO), 15.9 (HOC (CH ₃₎ COO). GC-MS: m / z = 176.07 for [lactyl-lactate-Me] ⁺ .

Example 7. Preparation of 1-methoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and methanol and HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of methanol (0.12 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-methoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.34 g (7.60 mmol, 99%). Elemental analysis for C 7 H 12 O 5 (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.7; H, 6.7. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.03 (q, = 7.1 Hz, 1H, OC77 (Me) COO), 4.31 (q, J _H -h =

7.0 Hz, 1H, HOC / R (Me)), 3.72 (br s, 1H, HO), 3.32 (s, 3H, COOCHfi 1.46 (d, 7-H _H = 7.1 Hz, 3H, OCH (CM ₃ ) COO), 1.20 (d, J _H -h = 7.1 Hz, 3H, HOCH (Ct H)) ¹³ C NMR (125 MHz, C ₅ D ₆ , 298K) : δ

176.5 (COOMe), 171.2 (C (Me) COO), 69.8 (OC (Me) COOMe), 67.4 (HOC (Me)), 52.1 (COOCH ₃ ), 20.7 (OC (CH ₃₎ COO), 16.3 (HOC (CH ₃₎ COO). GC-MS: m / z = 176.07 for [Iactyl lactate-Me] ⁺ .

Example 8. Preparation of 1-methoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and methanol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 mL of methanol (0.12 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-methoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.32 g (7.49 mmol, 98%). Elemental analysis for C 7 H 12 O 5 (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.6; H, 6.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.03 (q, J _H -h = 7.1 Hz, 1H, OC 7 / (Me) COO), 4.31 (q, J _H) - _H = 7.0 Hz, 1H, HOC (Me), 3.72 (br s, 1H, HO), 3.32 (s, 3H, COOC / 5), 1.46 (d, 7 _H -h = 7.1 Hz, 3H, OCH (CTC) COO), 1.20 (d, J _H -h = 7.1 Hz, 3H, HOCH (CM 3)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

176.5 (COOMe), 171.2 (C (Me) COO), 69.8 (OC (Me) COOMe), 67.4 (HOC (Me)), 52.1 (COOCH ₃ ), 20.7 (OC (CH ₃₎ COO), 16.3 (HOC (CH ₃₎ COO). GC-MS: w / z = 176.07 for [Iactyl lactate-Me] ⁺ .

Example 9. HI-initiated preparation of 1-methoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and methanol

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of methanol (0.12 mol) + 0.05 mL of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

-6GB 306988 B6

The yield of 1-methoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.34 g (7.60 mmol, 98%). Elemental analysis for C 7 H 12 O 5 (%): C, 47.72; H, 6.87; O, 45.41. Found: C, 47.9; H, 6.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.03 (q, J _H -h = 7.1 Hz, 1H, OCZf (Me) COO), 4.31 (q, J _H -h) = 1.0 Hz, 1H, HOCH (Me)), 3.72 (br s, 1H, HO), 3.32 (s, 3H, COOC / 7), 1.46 (d, 7 = _H -H 7.1 Hz, 3H, OCH (CH3) COO), 1.20 (d, _JH-H = 7.1 Hz, 3H, HOCH (CH3)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

176.5 (COOMe), 171.2 (C (Me) COO), 69.8 (OC (Me) COOMe), 67.4 (HOC (Me)), 52.1 (COOCH 3), 20.7 ( OC (CH ₃₎ COO), 16.3 (HOC (CH ₃₎ COO). GC-MS: m / z = 176.07 for [lactyl-lactate-Me] ⁺ .

Example 10. Preparation of (2S) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2S) -2-hydroxypropanoate from L-lactide and propan-2-ol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution consisting of 5 mL of propan-2-ol (isopropanol, 0.065 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2S) -2-hydroxypropanoate was 1.43 g (7.00 mmol, 92%). Elemental analysis for C 9 H 16 O 5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.7; H, 7.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 4.99 (q, J _H -h = 8.8 Hz, 1H, OCH (Me) COO),

4.90 (m, J _H -h = 7.8 Hz, 1H, CH (Me) ₂ ), 4.31 (q, J _H -h = 8.7 Hz, 1H, HOCH (Me)), 1 .47 (d, J _H-H =

8.7 Hz, 3H, OCH (C7c) COO), 1.21 (d, = 8.9 Hz, 3H, HOCH (CH _3), 0.98-0.96 (m, 6H,

CH (Cf 6) ₂ ). ¹³ C NMR (125 MHz, C ₅ D ₆ , 298K): δ 175.6 (COO'Pr), 170.4 (C (Me) COO), 70.0 (OC (Me) COO'Pr), 69 5 (HOC (Me)), 67.4 (CH (Me) ₂ ), 21.7 (CH (CH ₃ ) ₂ ), 20.9 (OC (CH ₃ ) COO),

16.9 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 11. Preparation of (2S) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2S) -2-hydroxypropanoate from L-lactide and propan-2-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of L-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of propan-2-ol (isopropanol, 0.065 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2S) -2-hydroxypropanoate was 1.40 g (6.86 mmol, 90%). Elemental analysis for C ₉ H ₁₆ O ₅ (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.9; H, 8.0. ^l H NMR (500 MHz, C ₆ D _6, 298K) δ 4.99 (q, 7 _H -H = 8.8 Hz, 1H, OCtf (Me) COO)

4.90 (m, 7 _H -H = 7.8 Hz, 1H, CH (Me) _2), 4.31 (q, .7 _H-H = 8.7 Hz, 1H, HOCtf (Me)) 1.47 (d, 7 = _H -H

8.7 Hz, 3H, OCH (C 1 H) COO), 1.21 (d, J _H + = 8.9 Hz, 3 H, HOCH (C 1 H)), 0.98-0.96 (m, 6H) CH (CI6) _2). ^l3 C NMR (125 MHz, C ₆ D _6, 298K): δ 175.6 (COO'Pr), 170.4 (C (Me) COO), 70.0 (OC ( Me) (COO (Pr)), 69.5 (HOC (Me)), 67.4 (CH (Me) ₂ ), 21.7 (CH (CH ₃ ) ₂ ), 20.9 (OC (CH ₃ ) COO )

16.9 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

-7EN 306988 B6

Example 12. Preparation of (2S) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2S) -2-hydroxypropanoate from L-lactide and propan-2-ol initiated by H1

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution consisting of 5 ml of propan-2-ol (isopropanol, 0.065 mol) + 0.05 ml of H1 (horse, 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2S) -2-hydroxypropanoate was 1.41 g (6.90 mmol, 90%). Elemental analysis for C ₉ H ₁₆ O ₅ (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.6; H, 7.9. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 4.99 (q, = 8.8 Hz, 1H, OC77 (Me) COO),

4.90 (m, J _H -h = 7.8 Hz, 1H, Ctf (Me) ₂ ), 4.31 (q, J _H -h = 8.7 Hz, 1H, HOCtf (Me)), 1 .47 (d, J _H-H =

8.7 Hz, 3H, OCH (C 6 H) COO), 1.21 (d, J / _H = 8.9 Hz, 3 H, HOCH (C / F), 0.98-0.96 (m, 6H, CH (C / FI) 2). ^'3 C NMR (125 MHz, C ₆ D _6, 298K): δ 175.6 (COO'Pr), 170.4 (C (Me) COO) , 70.0 (OC (Me) COO'Pr), 69.5 (HOC (Me)), 67.4 (CH (Me) ₂ ), 21.7 (CH (CH ₃ ) ₂ ), 20.9 (OC (CH ₃₎ COO)

16.9 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 13. Preparation of (2R) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2R) -2-hydroxypropanoate from D-lactide and propan-2-ol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution consisting of 5 mL of propan-2-ol (isopropanol, 0.065 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2A) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2 R) -2-hydroxypropanoate was 1.43 g (7.00 mmol, 92%). Elemental analysis for C 9 H 16 O 5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.7; H, 7.8. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.06 (q, 7 _{Η -η} = 8.0 Hz, 1H, OCH (Me) COO)

4.88 (m, _JH- h = 7.1 Hz, 1H, Ctf (Me) ₂ ), 4.25 (q, _JH- h = ⁸ Hz, ^1H , HOCtf (Me)), 1.42 (d, J _H-H =

7.2 Hz, 3H, OCH (CH3) COO), 1.20 (d, _JH-H = 8.9 Hz, 3H, HOCH (C / F)), 0.94-0.91 (m, 6H, CH (CH3) ₂ ). ¹³ C NMR (125 MHz, C ₆ D ₅ , 298K): δ 175.6 (COO'Pr), 170.1 (C (Me) COO), 70.5 (OC (Me) COO'Pr), 69 4 (HOC (Me)), 67.2 (CH (Me) ₂ ), 21.5 (CH (CH ₃ ) ₂ ), 20.2 (OC (CH ₃ ) COO),

16.6 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 14. Preparation of (2R) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2R) -2-hydroxypropanoate from D-lactide and propan-2-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of propan-2-ol (isopropanol, 0.065 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (R) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2H) -2-hydroxypropanoate was 1.40 g (6.86 mmol, 90%). Elemental analysis for C 8 H 10 O 6 O (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.9; H, 8.0. ¹ H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.06 (q, J _H -h = 8.0 Hz, 1H, OCH (Me) COO),

4.88 (m, 7 _H -h = 7.1 Hz, 1H, C H (Me) ₂ ), 4.25 (q, J _H -h = 8.0 Hz, 1H, HOCD (Me)) 1.42 (d, J _H-H =

-8GB 306988 Β6

7.2 Hz, 3H, OCH _(CH3) COO), 1.20 (d, Λτη = 8.9 Hz, 3H, HOCH (CH)), 0.94 to 0.91 (m, 6H, CH ( C / 6) ₂ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.6 (COO'Pr), 170.1 (C (Me) COO), 70.5 (OC (Me) COO'Pr), 69 4 (HOC (Me)), 67.2 (CH (Me) ₂ ), 21.5 (CH (CH ₃ ) ₂ ), 20.2 (OC (CH ₃ ) COO),

16.6 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 15. Preparation of (2R) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2R) -2-hydroxypropanoate from D-lactide and propan-2-ol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of isopropanol (0.065 mol) + 0.05 ml of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2R) -1-oxo-1- (propan-2-yloxy) propan-2-yl (2R) -2-hydroxypropanoate was 1.41 g (6.90 mmol, 91%). Elemental analysis for C 9 H 16 O 5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.6; H, 7.9. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.06 (q, J _{H- H} = 8.0 Hz, 1H, OC // (Me) COO),

4.88 (m, J H-H = 7.1 Hz, 1H, Ctf (Me) ₂ ), 4.25 (q, J _H-H = 8.0 Hz, 1H, HOCtf (Me)), 1, 42 (d, J / _H , i =

7.2 Hz, 3H, OCH _(CH3) COO), 1.20 (d, 7, _H = 8.9 Hz, 3H, HOCH (CH _3)), 0.94 to 0.91 (m, 6H CH (CH 3) ₂ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.6 (COO'Pr), 170.1 (C (Me) COO), 70.5 (OC (Me) COO'Pr), 69 4 (HOC (Me)), 67.2 (CH (Me) ₂ ), 21.5 (CH (CH ₃ ) ₂ ), 20.2 (OC (CH ₃ ) COO),

16.6 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 16. Preparation of 1-oxo-1- (propan-2-yloxy) propan-2-yl 2-hydroxypropanoate from rac-lactide and propan-2-ol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution consisting of 5 mL of propan-2-ol (isopropanol, 0.065 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-oxo-1- (propan-2-yloxy) propan-2-yl 2-hydroxypropanoate was 1.48 g (7.25 mmol, 95%). Elemental analysis for C ₉ H ₁₆ O ₅ (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.8; H, 8.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.03 (q, 7 _H -h = 7.2 Hz, 1H, OC77 (Me) COO), 4.79 (m, J _H- h = 7.0 Hz, 1H, CH (Me) ₂ ), 4.21 (q, J _H -h = 7.5 Hz, 1H, HOCH (Me)), 1.40 (d, J _H -h = 7.0 Hz, 3H, OCH (CTF ₃₎ COO), 1.23 (d, J _H .h = 7.2 Hz, 3H, HOCH (CTF _3)), from 0.95 to 0.92 (m 6H, CH _{(CH3) 2).} ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.0 (COO'Pr), 170.0 (C (Me) COO), 70.7 (OC (Me) COO'Pr), 69 5 (HOC (Me)), 67.4 (CH (Me) ₂ ), 21.8 (CH (CH ₃ ) ₂ ), 20.0 (OC (CH ₃ ) COO),

16.8 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 17. Preparation of 1-oxo-1- (propan-2-yloxy) propan-2-yl 2-hydroxypropanoate from rac-lactide and propan-2-ol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of propan-2-ol (isopropanol, 0.065 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

-9EN 306988 B6

The yield of 1-oxo-1- (propan-2-yloxy) propan-2-yl 2-hydroxypropanoate was 1.40 g (6.86 mmol, 90%). Elemental analysis for C ₉ H ₁₆ O ₅ (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.6; H, 8.1. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.03 (q, 7 _H -H = 7.2 Hz, 1H, OCtf (Me) COO), 4.79 (m, J _H - H = 7.0 Hz, 1 H, -OTf (Me) _2), 4.21 (q, 7 _H -H = 7.5 Hz, 3H, HOCH (CEG)), 1.40 (d, ./ _H - H = 7.0 Hz, 3H, OCH (C ^) COO), 1.23 (d, 7 _H -H = 7.2 Hz, 1H, HOCtf (Me)), 0.95 to 0.92 (m 6H, CH (C 1 H ₂ ). ¹³ C NMR (125 MHz, C ₆ D _6, 298K): δ 176.0 (COO'Pr), 170.0 (C (Me) COO), 70.7 (OC (Me) COO'Pr), 69, 5 (HOC (Me)), 67.4 (CH (Me) ₂ ), 21.8 (CH (CH ₃ ) ₂ ), 20.0 (OC (CH ₃ ) COO),

16.8 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 18. Preparation of 1-oxo-1- (propan-2-yloxy) propan-2-yl 2-hydroxypropanoate from rac-lactide and propan-2-ol initiated by HI

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution consisting of 5 ml of propan-2-ol (isopropanol, 0.065 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-oxo-1- (propan-2-yloxy) propan-2-yl 2-hydroxypropanoate was 1.41 g (6.90 mmol, 90%). Elemental analysis for C 9 H 16 O 5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.9; H, 7.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.03 (q, 7 _H -h = 1.2 Hz, 1H, OC // (Me) COO), 4.79 (m, 7 _H- h = 7.0 Hz, 1H, Ctf (Me) ₂ ), 4.21 (q, J = 7.5 Hz, 1H, HOC / 7 (Me)), 1.40 ( d, 7 _{H. H} = 7.0 Hz, 3H, OCH (C77j) COO), 1.23 (d, 7 _H _ _H = 7.2 Hz, 3H, HOCH (C //)), 0, 95-0.92 (m, 6H, CH (C ₁ H) ₂ ). ¹³ C NMR (125 MHz, C ₆ D _6, 298K): δ 176.0 (COO'Pr), 170.0 (C (Me) COO), 70.7 (OC (Me) COO'Pr), 69, 5 (HOC (Me)), 67.4 (CH (Me) ₂ ), 21.8 (CH (CH ₃ ) ₂ ), 20.0 (OC (CH ₃ ) COO),

16.8 (HOC (CH ₃₎ COO). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 19. Preparation of (2S) -1-tert-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from Llactide and 2-methylpropan-2-ol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of 7-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 S) -1-tert-butoxy-1-oxopropan-2-yl (2 S) -2-hydroxypropanoate was 1.50 g (6.87 mmol, 90%). Elemental analysis for C ₁₀ H ₈ O ₅ (%): C, 52.03; H, 8.31; O, 36.65. Found: C, 51.9; H, 8.2. H NMR (500 MHz, C ₆ D _6, 298K) δ 4.94 (q, 7 _H _ _H = 7.1 Hz, 1H, O // (Me) COO)

4.14 (q, 7 ,,,, = 6.9 Hz, 1H, HOC7 / (Me)), 1.38 (d, 7 _{H "H} = 6.9 Hz, 3H, OCH (Ctfj) COO) , 1.12 (d, J _H -H = 7.1 Hz, 3H, HOCH _(7/3)), 1.06 (s, 9H, C (CH3) _3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.7 (COO'Bu), 168.3 (C (Me) COO), 80.3 (C (Me) ₃ ), 69.5 (OC (Me) COO'Bu), 67.3 (HOC ( Me)),

31.2 (C (CH ₃ ) ₃ ), 20.8 (OC (CH ₃ ) COO), 16.7 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

- 10GB 306988 B6

Example 20. Preparation of (2S) -1-tert-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from Llactide and 2-methylpropan-2-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-tert-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.50 g (6.88 mmol, 90%). Elemental analysis for C 10 H 18 O 5 (C): C, 52.03; H, 8.31; O, 36.65. Found: C, 51.9; H, 8.3. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 4.94 (q, J _H -h = 7.1 Hz, 1H, OCf (Me) COO),

4.14 (q, J _H -h = 6.9 Hz, 1H, HOCt (Me)), 1.38 (d, J _H -h = 6.9 Hz, 3H, OCH (C7 / ₃ ) COO) , 1.12 (d, J _H -H = 7.1 Hz, 3H, HOCH (C7ř _5)), 1.06 (s, 9H, C (C / 7 _{3) 3).} ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.7 (COO'Bu), 168.3 (C (Me) COO), 80.3 (C (Me) ₃ ), 69.5 (OC (Me) COO'Bu), 67.3 (HOC ( Me)),

31.2 (C (CH ₃ ) ₃ ), 20.8 (OC (CH ₃ ) COO), 16.7 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 21. Preparation of (2S) -1-tert-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from Llactide and 2-methylpropan-2-ol initiated by H1

A 25 mL round bottom flask was charged with 1.1 g of β-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution consisting of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-tert-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.50 g (6.88 mmol, 90%). Elemental analysis for C ₁₀ H ₈ O ₅ (%): C, 52.03; H, 8.31; O, 36.65. Found: C, 51.9; H, 8.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 4.94 (q, J _H -h = ¹ Hz, 1H, OC77 (Me) COO),

4.14 (q, J _H-H = 6.9 Hz, 1H, HOC 7 O (Me)), 1.38 (d, J _H -6.9 = 6.9 Hz, 3H, OCH (C 1 H) COO), 1 12 (d, J H-H = 7.1 Hz, 3H, HOCH (C / £ _3)), 1.06 (s, 9H, C (7 £ _{3) 3).} ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.7 (COO'Bu), 168.3 (C (Me) COO), 80.3 (C (Me) ₃ ), 69.5 (OC (Me) COO'Bu), 67.3 (HOC ( Me)),

31.2 (C (CH ₃ ) ₃ ), 20.8 (OC (CH ₃ ) COO), 16.7 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 22. Preparation of (2R) -1-tert-butoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from Dlactide and 2-methylpropan-2-ol initiated by HCl

A 25 mL round bottom flask was charged with 1.1 g of ε-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (R) -1- tert -butoxy-1-oxopropan-2-yl (2 H) -24-hydroxypropanoate was 1.45 g (6.64 mmol, 87%). Elemental analysis for C ₁₀ H ₁₈ O ₅ (%): C, 52.03; H, 8.31; O, 36.65. Found: C, 52.1; H, 8.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 4.90 (q, J _H -h = 7.5 Hz, 1H, OC 7 (Me) COO), 4.08 (q, Λ, -η = 8.2 Hz, 1H, HOC 7 (Me)), 1.41 (d, = 7.7 Hz, 3H, OCH ( _C 7 → ₃ ) COO), 1.19 (d,

- 11 GB 306988 B6

J _H -H = 7.5 Hz, 3H, HOCH _(7/5)), 1.02 (s, 9H, C (CTF _{3) 3).} ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.5 (COO'Bu), 169.3 (C (Me) COO), 80.5 (C (Me) ₃ ), 69.7 (OC (Me) COO'Bu), 67.5 (HOC ( MeI), 32.0 (C (CH ₃ ) ₃ ), 21.0 (OC (CH ₃ ) COO), 16.2 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 23. Preparation of (2R) -1-tert-butoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from Dlactide and 2-methyl propan-2-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 R) -1-tert-butoxy-1-oxopropan-2-yl (2 R) -2-hydroxypropanoate was 1.48 g (6.78 mmol, 89%). Elemental analysis Οι ₀ Ηι ₈ Ο ₅ (%): C, 52.03; H, 8.31; O, 36.65. Found: C, 51.8; H, 8.4. * H NMR (500 MHz, C ₆ D _6, 298K) δ 4.90 (q, J _H-H = 7.5 Hz, 1H, OC / 7 (Me) COO), 4.08 (q, J _H H = 8.2 Hz, 1H, HOCtf (Me)), 1.41 (d, 7 _H -H = 7.7 Hz, 3H, OCH _(7/3) COO), 1.19 (d, J _H _ _H = 7.5 Hz, 3H, HOCH (C // _3)), 1.02 (s, 9H, C (CH3) _3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.5 (COO'Bu), 169.3 (C (Me) COO), 80.5 (C (Me) ₃ ), 69.7 (OC (Me) COO'Bu), 67.5 (HOC ( MeI), 32.0 (C (CH ₃ ) ₃ ), 21.0 (OC (CH ₃ ) COO), 16.2 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 24. Preparation of (2R) -1-tert-butoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from Dlactide and 2-methylpropan-2-ol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution consisting of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 R) -1-tert-butoxy-1-oxopropan-2-yl (2 R) -2-hydroxypropanoate was 1.50 g (6.88 mmol, 90%). Elemental analysis for C ₁₀ H ₁₈ O ₅ (%): C, 52.03; H, 8.31; O, 36.65. Found: C, 51.6; H, 8.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 4.90 (q, J _H -h = 7.5 Hz, 1H, OCH (Me) COO), 4.08 (q, J _H- h = 8.2 Hz, 1 H, HOCH (Me)), 1.41 (d, Λ, n = 7.7 Hz, 3 H, OCH (C _{3 H} ) COO), 1.19 (d, 7 _H -h = 7.5 Hz, 3H, HOCH _(7/3)), 1.02 (s, 9H, C (CH) _3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.5 (COO'Bu), 169.3 (C (Me) COO), 80.5 (C (Me) ₃ ), 69.7 (OC (Me) COO'Bu), 67.5 (HOC ( MeI), 32.0 (C (CH ₃ ) ₃ ), 21.0 (OC (CH ₃ ) COO), 16.2 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu].

Example 25. Preparation of 1-tert-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and 2-methyl propan-2-ol initiated with HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

- 12GB 306988 B6

The yield of 1- tert -butoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.53 g (7.01 mmol, 92%). Elemental analysis for C 10 H 18 O 5 (%): C, 52.03; H, 8.31; O, 36.65. Found: C, 52.3; H, 8.5. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.0 Hz, 1H, OCH (Me) COO), 4.18 (q, J _H- h =

6.7 Hz, 1H, HOC7 / (Me)), 1.40 (d, J _H -H = 6.8 Hz, 3H, OCH (CTF ₃₎ COO), 1.19 (d, J _{N H} _ = 7.0 Hz, 3H, HOCH (C77 ₃₎₎ Ι, θθ (s, 9H, C (CTF _{3) 3).} ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.4 (COO'Bu),

169.2 (C (Me) COO), 80.9 (C (Me) ₃ ), 69.2 (OC (Me) COO'Bu), 68.0 (HOC (Me)), 31.1 (C (CH3) ₃₎

21.1 (OC (CH ₃ ) COO), 16.7 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 26. Preparation of 1-tert-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and 2-methyl propan-2-ol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- tert -butoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.52 g (6.96 mmol, 91%). Elemental analysis for C ₁₀ H ₁₈ O ₅ (%): C, 52.03; H, 8.31; O, 36.65. Found: C, 51.8; H, 8.3. * HNMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.0 Hz, 1H, OC77 (Me) COO), 4.18 (q, J _H -h) =

6.7 Hz, 1H, HOCt (Me)), 1.40 (d, J _H -h = 6.8 Hz, 3H, OCH (C 77 ₃ ) COO), 1.19 (d, J _H -h = 7.0 Hz, 3H, HOCH (C7 / ₃ )), 1.00 (s, 9H, C (CT / ₃ ) ₃ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.4 (COO'Bu),

169.2 (C (Me) COO), 80.9 (C (Me) ₃ ), 69.2 (OC (Me) COO'Bu), 68.0 (HOC (Me)), 31.1 (C (CH3) ₃₎

21.1 (OC (CH ₃ ) COO), 16.7 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 27. Preparation of 1-tert-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and 2-methyl propan-2-ol initiated by HI

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution consisting of 5 ml of 2-methyl propan-2-ol (tert-butanol, 0.052 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. . All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- tert -butoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.49 g (6.83 mmol, 89%). Elemental analysis for C ₁₀ H ₁₈ O ₅ (%): C, 52.03; H, 8.31; O, 36.65. Found: C, 51.5; H, 8.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.0 Hz, 1H, OC77 (Me) COO), 4.18 (q, 7 _H h =

6.7 Hz, 1H, HOC / 7 (Me)), 1.40 (d, J _H-H = 6.8 Hz, 3H, OCH (C ₇ H ₃ ) COO), 1.19 (d, J _H - H = 7.0 Hz, 3H, HOCH _(7/3)), 1.00 (s, 9H, C (CH3) _3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.4 (COO'Bu),

169.2 (C (Me) COO), 80.9 (C (Me) ₃ ), 69.2 (OC (Me) COO'Bu), 68.0 (HOC (Me)), 31.1 (C (CH3) ₃₎

21.1 (OC (CH ₃ ) COO), 16.7 (HOC (CH ₃ ) COO). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 28. Preparation of (2S) -1-oxo-1-propoxypropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and propan-1-ol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added,

And the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1-propoxypropan-2-yl (2S) -2-hydroxypropanoate was 1.54 g (7.54 mmol, 99%). Elemental analysis for C 9 H 16 O 5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.7; H, 8.0. * HNMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.1 Hz, 1H, OC / 7 (Me) COO), 4.32 (q, Z ' _H = 6.9 Hz, 1H, HOCH (Me)), 3.84 (m, J _H-H = 6.8 Hz, 2H, C H ₂ CH ₂ CH ₃ ), 1.47 (d, J _{H. H} = 6.9 Hz, 3H, OCH (CH) COO), 1.35-1.31 (m, 2H, CH ₂ C / 7 ₂ CH _3), 1.23 (d, J _H -H = 7.1 Hz, 3H, HOCH (C77 _3),), 0.65 (t, J _H-H = 6.8 Hz, 1H, CH ₂ CH ₂ C _7/3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.6 (COOPr), 170.9 (C (Me) COO), 69.8 (OC (Me) COOPr), 67.4 (HOC (Me)), 67.1 (CH ₂ CH ₂ CH ₃ ) , 22.4 (OC (CH ₃ ) COO), 20.9 (CH ₂ CH ₂ CH ₃ ), 17.1 (HOC (CH ₃ ) COO), 10.6 (CH ₂ CH ₂ CH ₃ ). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 29. Preparation of (2S) -1-oxo-1-propoxypropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and propan-1-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1-propoxypropan-2-yl (2S) -2-hydroxypropanoate was 1.53 g (7.49 mmol, 98%). Elemental analysis for CcJOs (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.8; H, 7.9. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.1 Hz, 1H, OCH (Me) COO), 4.32 (q, Z _H- h =

6.9 Hz, 1 H, HOC 2 Z (Me)), 3.84 (m, J _H -h = 6.8 Hz, 2H, CH ₂ CH ₂ CH ₃ ), 1.47 (d, Z _{H- H} = 6 9 Hz, 3H, OCH (C H ₂ O COO), 1.35-1.31 (m, 2H, CH ₂ C H ₂ CH ₃ ), 1.23 (d, J _H + = 7.1 Hz, 3H, HOCH (CTF _3)), 0.65 (t, J _H-H = 6.8 Hz, 1H, CHzCHjC ^). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 175.6 (COOPr),

170.9 (C (Me) COO), 69.8 (OC (Me) COO'Pr), 67.4 (HOC (Me)), 67.1 (CH ₂ CH ₂ CH ₃ ), 22.4 (OC) (CH ₃ ) COO), 20.9 (CH ₂ CH ₂ CH ₃ ), 17.1 (HOC (CH ₃ ) COO), 10.6 (CH ₂ CH ₂ CH ₃ ). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 30. Preparation of (2S) -1-oxo-1-propoxypropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and propan-1-ol initiated by H1

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1-propoxypropan-2-yl (2S) -2-hydroxypropanoate was 1.54 g (7.55 mmol, 99%). Elemental analysis C \ H] _D drawbar (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 53.0; H,

8.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.1 Hz, 1H, OCZ 7 (Me) COO), 4.32 (q, J _H h) = 6.9 Hz, 1H, HOC 77 (Me)), 3.84 (m, Z _{H- H} = 6.8 Hz, 2H, C ₇ Z ₂ CH ₂ CH ₃ ), 1.47 (d, J H = 6 9 Hz, 3H, OCH (CZG) COO), 1.35-1.31 (m, 2H, CH ₂ C / ZCH _3), 1.23 (d, Z _H -H = 7.1 Hz, 3H , HOCH _(7/3)), 0.65 (t, ./,,-11 = 6.8 Hz, 1H, CH ₂ CH ₂ C / 7 _3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.6 (COO Pr), 170.9 (C (Me) COO), 69.8 (OC (Me) COOPr), 67.4 (HOC (Me)), 67.1

-14EN 306988 B6 (CH ₂ CH ₂ CH ₃ ), 22.4 (OC (CH ₃ ) COO), 20.9 (CH ₂ CH ₂ CH ₃ ), 17.1 (HOC (CH ₃ ) COO), 10 6 (CH ₂ CH ₂ CH ₃ ). GC-MS: m / z = 204.10 for [L-lactyl-L-Pr] ⁺ .

Example 31. Preparation of (2R) -1-oxo-1-propoxypropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and propan-1-ol initiated by HCl

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2R) -1-oxo-1-propoxypropan-2-yl (2 R) -2-hydroxypropanoate was 1.53 g (7.49 mmol, 98%). Elemental analysis for C ₉ H ₁₁ N ₃ O _{2 6} O5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.7; H, 8.0. Those NMR (500 MHz, C ₆ D _6, 298K) δ 5.11 (q, 7 _H -H = 7.0 Hz, 1H, OCtf (Me) COO), 4.47 (q, J _H-H = 7.0 Hz, 1H, HOCtf (Me)), 3.78 (m, J _H-H = 7.2 Hz, 2H, CH ₂ CH ₂ CH _3), 1.49 (d, J _H -H = 7.1 Hz, 3H, OCH (C ₇ -C ₃ ) COO), 1.33-1.27 (m, 2H, CH ₂ CH ₂ CH ₃ ), 1.22 (d, J _H -h = 7.0 Hz) , 3H, HOCH _(7/3)), 0.66 (t, ./"_ _H = 7.0 Hz, 1H, CH ₂ CH ₂ C // _3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

176.2 (COO ^fl Pr), 171.3 (C (Me) COO), 69.6 (OC (Me) COOPr), 67.1 (HOC (Me)), 67.8 (CH ₂ CH ₂ CH ₃ ), 22.9 (OC (CH ₃ ) COO), 21.0 (CH ₂ CH ₂ CH ₃ ), 16.5 (HOC (CH ₃ ) COO), 10.7 (CH ₂ CH ₂ CH ₃ ) . GC-MS: m / z = 204.10 for [lactyl-lactate-Pr],

Example 32. Preparation of (2Rγ-1-oxo-1-propoxypropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and propan-1-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2R) -1-oxo-1-propoxypropan-2-yl (2R) -2-hydroxypropanoate was 1.51 g (7.39 mmol, 97%). Elemental analysis for C 9 H 16 O 5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.8; H, 7.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.11 (q, J _{f [[ H} = 7.0 Hz, 1H, OCH (Me) COO), 4.47 (q, J _{H) H} = 7.0 Hz, 1H, HOCH (Me)), 3.78 (m, _1H-H = 7.2 Hz, 2H, C 77 ₂ CH ₂ CH ₃ ), 1.49 (d, J _H-H = 7.1 Hz, 3H, OCH (C / 7 ₃₎ COO), 1.33 to 1.27 (m, 2H, CH ₂ CH ₂ -OTf _3), 1.22 (d, ./ _H - "= 7.0 Hz, 3H, HOCH _(7/3)), 0.66 (t, Vin = 7.0 Hz, 1H, CH ₂ CH ₂ C77 _3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

176.2 (COOPr), 171.3 (C (Me) COO), 69.6 (OC (Me) COOPr), 67.1 (HOC (Me)), 67.8 (CH ₂ CH ₂ CH ₃ ) , 22.9 (OC (CH ₃ ) COO), 21.0 (CH ₂ CH ₂ CH ₃ ), 16.5 (HOC (CH ₃ ) COO), 10.7 (CH ₂ CH ₂ CH ₃ ). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 33. Preparation of (2R) -1-oxo-1-propoxypropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and propan-1-ol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

- 15 GB 306988 B6

The yield of (2 R) -1-oxo-1-propoxypropan-2-yl (2 R) -2-hydroxypropanoate was 1.54 g (7.55 mmol, 99%). Elemental analysis for C ₉ H ₁₆ O ₅ (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 53.0; H,

8.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.11 (q, J _H -h = 7.0 Hz, 1H, OC // (Me) COO), 4.47 (q, J _{H H} = 7.0 Hz, 1H, HOC 7 O (Me)), 3.78 (m, J _H -h = 7.2 Hz, 2H, C ₁ H ₂ CH ₂ CH ₃ ), 1.49 (d, J). _H-H = 7.1 Hz, 3H, OCH (C / 7 ₃₎ COO), 1.33 to 1.27 (m, 2H, CH ₂ C // ₂ CH _3), 1.22 (d, J _H- h = 7.0 Hz, 3H, HOCH (C ₇ H ₃ )), 0.66 (t, J _H -h = 7.0 Hz, 1H, CH ₂ CH ₂ CH ₃ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

176.2 (COOPr), 171.3 (C (Me) COO), 69.6 (OC (Me) COOPr), 67.1 (HOC (Me)), 67.8 (CH ₂ CH ₂ CH ₃ ) , 22.9 (OC (CH ₃ ) COO), 21.0 (CH ₂ CH ₂ CH ₃ ), 16.5 (HOC (CH ₃ ) COO), 10.7 (CH ₂ CH ₂ CH ₃ ). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] '.

Example 34. Preparation of 1-oxo-1-propoxypropan-2-yl 2-hydroxypropanoate from rac-lactide and propan-1-ol initiated with HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-oxo-1-propoxypropan-2-yl 2-hydroxypropanoate was 1.54 g (7.58 mmol, 99%). Elemental analysis for C ₉ H ₁₆ O ₅ (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 53.2; H, 8.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.08 (q, A, J = 7.2 Hz, 1H, OC77 (Me) COO), 4.43 (q, J _H) h =

6.9 Hz, 1H, HOCtf (Me)), 3.75 (m, λm = 7.0 Hz, 2H, Ctf ₂ CH ₂ CH ₃ ), 1.43 (d, J _H -h = 7.0 Hz, 3H, OCH (C77 ₃₎ COO), 1.33-1.28 (m, 2H, CH ₂ C // ₂ CH _3), 1.23 (d, 7 _H -H = 7.0 Hz, 3H, HOCH (C 77 H), 0.59 (t, Al ₁ = 7.0 Hz, 1H, CH ₂ CH ₂ Cl ₃ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 176.0 (COO Pr),

171.5 (C (Me) COO), 69.0 (OC (Me) COOPr), 66.2 (HOC (Me)), 67.1 (CH ₂ CH ₂ CH ₃ ), 21.3 (OC (Me) CH ₃ ) COO), 20.2 (CH ₂ CH ₂ CH ₃ ), 16.4 (HOC (CH ₃ ) COO), 10.6 (CH ₂ CH ₂ CH ₃ ). GC-MS: m / z - 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 35. Preparation of 1-oxo-1-propoxypropan-2-yl 2-hydroxypropanoate from rac-lactide and propan-1-ol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-oxo-1-propoxypropan-2-yl 2-hydroxypropanoate was 1.52 g (7.43 mmol, 97%). Elemental analysis for C 9 H 16 O 5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 52.9; H, 8.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.08 (q, J _H -h = 7.2 Hz, 1H, OC77 (Me) COO), 4.43 (q, J _H -h) =

6.9 Hz, 1H, HOCtf (Me)), 3.75 (m, J _H-H = 7.0 Hz, 2H, C / 7 ₂ CH ₂ CH _3), 1.43 (d, J _H - H = 7.0 Hz, 3H, OCH (C / 7 ₃₎ COO), 1.33-1.28 (m, 2H, CH ₂ C // ₂ CH _3), 1.23 (d, J _H - H = 7.0 Hz, 3H, HOCH (C / 7 _3)), 0.59 (t, J _H-H = 7.0 Hz, 1H, CH ₂ CH ₂ C // ₃₎ · ^'3 C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 176.0 (COO ”Pr),

171.5 (C (Me) COO), 69.0 (OC (Me) COOPr), 66.2 (HOC (Me)), 67.1 (CH ₂ CH ₂ CH ₃ ), 21.3 (OC (Me) CH ₃ ) COO), 20.2 (CH ₂ CH ₂ CH ₃ ), 16.4 (HOC (CH ₃ ) COO), 10.6 (CH ₂ CH ₂ CH ₃ ). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

-16GB 306988 B6

Example 36. Preparation of 1-oxo-1-propoxypropan-2-yl 2-hydroxypropanoate from rac-lactide and propan-1-ol initiated by HI

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of propan-1-ol (0.067 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-oxo-1-propoxypropan-2-yl 2-hydroxypropanoate was 1.53 g (7.49 mmol, 98%). Elemental analysis for C 9 H 16 O 5 (%): C, 52.93; H, 7.90; O, 39.17. Found: C, 53.0; H, 8.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.08 (q,, / _H -h = 7.2 Hz, 1H, OCtf (Me) COO), 4.43 (q, J _H - h =

6.9 Hz, 1H, HOC 77 (Me)), 3.75 (m, J _H -h = 7.0 Hz, 2H, CH ₂ CH ₂ CU ₃ ), 1.43 (d, J _H -h = 7.0 Hz, 3H, OCH (CEfi) COO), 1.33-1.28 (m, 2H, CH ₂ C77 _{2 CH3),} 1.23 (d, 7 _H -H = 7.0 Hz, 3H, HOCH (C H ₃ )), 0.59 (t, J _H -h = 7.0 Hz, 1H, CH ₂ CH ₂ Cl ₃ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 176.0 (COO Pr),

171.5 (C (Me) COO), 69.0 (OC (Me) COOPr), 66.2 (HOC (Me)), 67.1 (CH ₂ CH ₂ CH ₃ ), 21.3 (OC (Me) CH ₃ ) COO), 20.2 (CH ₂ CH ₂ CH ₃ ), 16.4 (HOC (CH ₃ ) COO), 10.6 (CH ₂ CH ₂ CH ₃ ). GC-MS: m / z = 204.10 for [lactyl-lactate-Pr] ⁺ .

Example 37. Preparation of (2S) -1-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and butan-1-ol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-butoxy-1-oxopropan-2-yl (2 S) -2-hydroxypropanoate was 1.64 g (7.51 mmol, 98%). Elemental analysis for C ₁₀ H ₈ O ₅ (%): C, 55.03; H, 8.31; O, 36.65. Found: C, 54.9; H,

8.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.04 (q,, 1 _H -h = 7.1 Hz, 1H, OCH (Me) COO), 4.60 (br s, 1H DOC (Me)), 4.33 (q, _JH- h = 6.9 Hz, 1H, HOCtf (Me)), 3.90 (m, .7H- _h = 6.2 Hz, 2H, C7 / ₂ CH ₂ CH ₂ CH _3), 1.48 (d, J _H -H = 7.0 Hz, 3H, OCH (CH₃) COO), 1.31-1.28 (m, 2H, CH ₂ CH ₂ CH ₂ CH _3), 1.23 (d, J _H -H = 7.1 Hz, 3H, HOCH (CTF _3)), 1.12-1.08 (m, J _HH = 7.8 Hz, 2H, _{(CH2) 2} C7 / _{2 CH3),} 0.71 (t, J _H-H = 7.4 Hz, 3H _{(CH2) 3 CH3).} ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.6 (COOBu), 170.9 (C (Me) COO), 69.8 (OC (Me) COOBu), 67.4 (HOC (Me)), 65.6 (CH ₂ (CH _{2) 2} CH ₃ ), 31.0 (CH ₂ CH ₂ CH ₂ CH ₃ ), 20.9 (OC (CH ₃ ) COO), 19.5 ((CH ₂ ) ₂ CH ₂ CH ₃ ), 17.1 (HOC (CH ₃ ) COO), 14.0 ((CH ₂ ) ₃ CH ₃ ). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 38. Preparation of (2S) -1-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and butan-1-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml HBr (conc. 48%, 0.44 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2/7) -1-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.66 g (7.60 mmol, 99%). Elemental analysis for C ₁₀ H ₈ O ₅ (%): C, 55.03; H, 8.31; O, 36.65. Found: C, 55.2; H,

- 17 GB 306988 B6

8.5. 1 H NMR (500 MHz, C ₅ D ₆ , 298K): δ 5.04 (q, J _H -h = 7.1 Hz, 1H, OC 77 (Me) COO), 4.60 (br s, 1H, 77OC (Me)), 4.33 (q, J _H -h = 6.9 Hz, 1H, HOC / 7 (Me)), 3.90 (m, J _H -h = 6.2 Hz, 2H, C77 ₂ CH ₂ CH ₂ CH _3), 1.48 (d, .7 _H-H = 7.0 Hz, 3H, OCH (C / 7 ₃₎ COO), 1.31-1.28 (m, 2H CH ₂ C // ₂ CH ₂ CH _3), 1.23 (d, J _H -H = 7.1 Hz, 3H, HOCH (C / 7 _3)), 1.12-1.08 (m, J _H = 7.8 Hz, 2H, (CH ₂ ) ₂ C / ₂ CH ₃ ), 0.71 (t, J _H = 7.4 Hz, 3 H, (CH ₂ ) ₃ C / 7) ₃ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ

175.6 (COOBu), 170.9 (C (Me) COO), 69.8 (OC (Me) COO-Bu), 67.4 (HOC (Me)), 65.6 (CH ₂ (CH ₂₎ ) ₂ CH _3), 31.0 (CH ₂ C / 7 ₂ CH ₂ CH _3), 20.9 (OC (CH ₃₎ COO), 19.5 ((CH _{2) 2} CH ₂ CH _3), 17 1 (HOC (CH ₃ ) COO), 14.0 ((CH ₂ ) ₃ CH ₃ ). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 39. Preparation of (2S) -1-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and butan-1-ol initiated by H1

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml H1 (conc. 67%, 0.51 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-butoxy-1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.62 g (7.42 mmol, 97%). Elemental analysis for C ₁₀ H ₁₈ O ₅ (%): C, 55.03; H, 8.31; O, 36.65. Found: C, 54.9; H, 8.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.04 (q, 7h _h = 7.1Hz, 1H, OCtf (Me) COO), 4.60 (br s, 1H, tfOC) (Me)), 4.33 (q, J _H-H = ^6, 9 Hz, 1H, HOC / 7 (Me)), 3.90 (m, J H-H = 6.2 Hz, 2H, C772CH2CH2CH3) 1.48 (d, JH-h = 7.0 Hz, 3H, OCH (C / 73) COO), 1.31-1.28 (m, 2H, CH2C / 72CH2CH3), 1.23 (d, JH) -h = 7.1 Hz, 3H, HOCH (C // 3)), 1.12-1.08 (m, J H-h = 7.8 Hz, 2H, (CH 2) 2 C / 2 CH 3), 0 71 (t, J H-H = 7.4 Hz, 3H, (CH 2) 3 Cl 3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ

175.6 (COOBu), 170.9 (C (Me) COO), 69.8 (OC (Me) COO-Bu), 67.4 (HOC (Me)), 65.6 (CH ₂ (CH ₂₎ ) ₂ CH _3), 31.0 (CH ₂ C / 7 ₂ CH ₂ CH _3), 20.9 (OC (CH ₃₎ COO), 19.5 ((CH _{2) 2} CH ₂ CH _3), 17 1 (HOC (CH ₃ ) COO), 14.0 ((CH ₂ ) ₃ CH ₃ ). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 40. Preparation of (2R) -1-butoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and butan-1-ol initiated by HCl

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 R) -1-butoxy-1-oxopropan-2-yl (2 H) -2-hydroxypropanoate was 1.64 g (7.51 mmol, 98%). Elemental analysis for C ₁₀ H ₈ O ₅ (%): C, 55.03; H, 8.31; O, 36.65. Found: C, 54.9; H,

8.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.19 (q, J _H -h = 8.0 Hz, 1H, OC77 (Me) COO), 4.13 (q, J _{H H)} = 7.5 Hz, 1H, HOC 77 (Me)), 3.74 (m, J _H-H = 7.5 Hz, 2H, C 77 ₂ (CH ₂ ) ₂ CH ₃ ), 1.52 (d, J _H-H = 6.8 Hz, 3H, OCH (C / 7 ₃₎ COO), 1.31-1.27 (m, 2H, CH ₂ C / 7 ₂ CH ₂ CH _3), 1.20 (d J _H -H = 7.0 Hz, 3H, HOCH (C / 7 _3)), 1.13 to 1.08 (m, J _H-H = 8.0 Hz, 2H, (CH _{2) 2} -OTf ₂ CH ₃ ), 0.70 (t, 7H = 7.1 Hz, 3H, (CH ₂ ) ₂ CH ₃ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.8 (COOBu), 168.7 (C (Me) COO), 71.2 (OC (Me) COOBu), 67.6 (HOC) (Me)), 65.8 (CH ₂ (CH ₂ ) ₂ CH ₃ ), 30.2 (CH ₂ C / ₂ CH ₂ CH ₃ ), 20.8 (OC (CH ₃ ) COO), 18, Δ ((CH ₂ ) ₂ CH ₂ CH ₃ ), 17.0 (HOC (CH ₃ ) COO), 12.7 ((CH ₂ ) ₃ CH ₃ ). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

- 18GB 306988 B6

Example 41. Preparation of (2R) -1-butoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and butan-1-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml HBr (conc. 48%, 0.44 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 R) -1-butoxy-1-oxopropan-2-yl (2A) -2-hydroxypropanoate was 1.62 g (7.42 mmol, 97%). Elemental analysis for C 10 H ₁₈ O 5: C, 55.03; H, 8.31; O, 36.65. Found: C, 54.7; H,

8.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.19 (q, J _H -h = 8.0 Hz, 1H, OC // (Me) COO), 4.13 (q, 7 _{[ ( H} = 7.5 Hz, 1H, HOC / 7 (Me)), 3.74 (m, J _H-H = 7.5 Hz, 2H, Ct H ₂ (CH ₂ ) ₂ CH ₃ ), 1.52 ( d, J _H -h = 6.8 ^Hz > 3H, OCH (CD ₃ ) COO), 1.31-1.27 (m, 2H, CH ₂ C / ₂ CH ₂ CH ₃ ), 1.20 ( d, J _H -h = 1.0 Hz, 3H, HOCH (CH ₃ )), 1.13-1.08 (m, = 8.0 Hz, 2H, (CH ₂ ) ₂ CD ₂ CH ₃ ), 0.70 (t, J _H-H = 7.1 Hz, 3H, (CH ₂ ) ₂ CD ₃ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.8 (COOBu), 168.7 (C (Me) COO), 71.2 (OC (Me) COOBu), 67.6 (HOC) (Me)), 65.8 (CH ₂ (CH ₂ ) ₂ CH ₃ ), 30.2 (CH ₂ CD ₂ CH ₂ CH ₃ ), 20.8 (OC (CH ₃ ) COO), 18.8 ( (CH ₂ ) ₂ CH ₂ CH ₃ ), 17.0 (HOC (CH ₃ ) COO), 12.7 ((CH ₂ ) ₃ CH ₃ ). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 42. Preparation of (2R) -1-butoxy-1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and butan-1-ol initiated by H1

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml H1 (conc. 67%, 0.51 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2A) -1-butoxy-1-oxopropan-2-yl (2A) -2-hydroxypropanoate was 1.66 g (7.60 mmol, 99%). Elemental analysis for C ₁₀ H ₈ O ₅ (%): C, 55.03; H, 8.31; O, 36.65. Found: C, 55.0; H,

8.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.19 (q, J _H -h = 8.0 Hz, 1H, OC f (Me) COO), 4.13 (q, J _{H H)} = 7.5 Hz, 1H, HOCH (Me)), 3.74 (m, J _H-H = 7.5 Hz, 2H, C / ₂ (CH ₂ ) ₂ CH ₃ ), 1.52 (d J _H -H = 6.8 Hz, 3H, OCH (C / 7 ₃₎ COO), 1.31-1.27 (m, 2H, CH ₂ CH ₂ -OTf ₂ CH _3), 1.20 (d 1 _H -h = 7.0 Hz, 3H, HOCH (CD ₃ )), 1.13-1.08 (m, J _HH = 8.0 Hz, 2H, (CH ₂ ) ₂ C / 7 ₂ CH ₃ ), 0.70 (t, J _H -h = 7.1 Hz, 3H, (CH ₂ ) ₂ CD ₃ ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.8 (COOBu), 168.7 (C (Me) COO), 71.2 (OC (Me) COOBu), 67.6 (HOC) (Me)), 65.8 (CH ₂ (CH _{2) 2} CH _3), 30.2 (CH ₂ C / I ₂ CH ₂ CH _3), 20.8 (OC (CH ₃₎ COO), 18, Δ ((CH ₂ ) ₂ CH ₂ CH ₃ ), 17.0 (HOC (CH ₃ ) COO), 12.7 ((CH ₂ ) ₃ CH ₃ ). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 43. Preparation of 1-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and butanl-ol initiated with HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

- 19GB 306988 B6

The yield of 1-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.65 g (7.56 mmol, 99%). Elemental analysis for C 10 H ₁₈ O ₅ (%): C, 55.03; H, 8.31; O, 36.65. Found: C, 54.8; H, 8.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.41 (q, J _H -h = 8.0 Hz, 1H, OC // (Me) COO), 4.38 (q, = 7.7 Hz, 1H, HOC (Me)), 3.77 (m, J _H-H = 7.8 Hz, 2H, C / 7 ₂ (CH ₂ ) ₂ CH ₃ ), 1.54 (d , 7.5 Hz,

3H, OCH (C / F ₃ COO), 1.39-1.32 (m, 2H, CH ₂ C / ₂ CH ₂ CH ₃ ), 1.31 (d, J _H -h = 7.5 Hz, 3H, HOCH (C / 7 _3)), 1.16 to 1.10 (m, J _H-H = 7.7 Hz, 2H, (CH _{2) 2} C // ₂ CH ₃₎ 0, 85 (t, J _H-H = 7.5 Hz, 3H _{(CH2) 3} C / ₃ 7). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 172.5 (COOBu), 166.3 (C (Me) COO), 73.9 (OC (Me) COOBu), 67.1 (HOC) (Me)), 63.2 (CH ₂ (CH ₂ ) ₂ CH ₃ ), 32.1 (CH ₂ C / ₂ CH ₂ CH ₃ ), 22.2 (OC (CH ₃ ) COO), 19, 2 ((CH ₂ ) ₂ CH ₂ CH ₃ ), 17.2 (HOC (CH ₃ ) COO), 15.7 ((CH ₂ ) ₂ CH ₃ ). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] \

Example 44. Preparation of 1-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and butan-1-ol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml HBr (conc. 48%, 0.44 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.65 g (7.56 mmol, 99%). Elemental analysis for C ₁₀ H ₁₈ O ₅ (%): C, 55.03; H, 8.31; O, 36.65. Found: C, 55.2; H, 8.6. NMR (500 MHz, C ₆ D _5, 298K) δ 5.41 (q, / _H-H = 8.0 Hz, 1Η, OC77 (Me) COO), 4.38 (q, 7 _H - h = 7.7 Hz, 1 H, HOC // (Me)), 3.77 (m, 7 _H -h = 7.8 Hz, ₂ H, C // ₂ (CH ₂ ) ₂ CH ₃ ), 1, 54 (d, J _H -H = 7.5 Hz, 3Η, OCH (C77 ₃₎ COO), 1.39 to 1.32 (m, 2H, CH ₂ C7 / ₂ CH ₂ CH _3), 1.31 (d, J _H -h = 7.5Hz, 3Η, HOCH (C 77 ₃ )), 1.16-1.10 (m, J _H -h = 7.7Hz, 2H, (CH ₂ ) ₂ C) // ₂ CH _2), 0.85 (t, Λι-η = 7.5 Hz, 3H _{(CH2) 3 7/3).} ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 172.5 (COOBu), 166.3 (C (Me) COO), 73.9 (OC (Me) COOBu), 67.1 (HOC) (Me)), 63.2 (CH ₂ (CH ₂ ) ₂ CH ₃ ), 32.1 (CH ₂ C / ₂ CH ₂ CH ₃ ), 22.2 (OC (CH ₃ ) COO), 19, 2 ((CH ₂ ) ₂ CH ₂ CH ₃ ), 17.2 (HOC (CH ₃ ) COO), 15.7 ((CH ₂ ) ₂ CH ₃ ). GC-MS: m / z - 218.11 for [lactyl-lactate-Bu] ⁺ .

Example 45. Preparation of 1-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and butanl-ol initiated by HI

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. A solution of butan-1-ol (0.054 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) was then added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-butoxy-1-oxopropan-2-yl 2-hydroxypropanoate was 1.62 g (7.42 mmol, 97%). Elemental analysis for C 10 H ₈ O ₅ (%): C, 55.03; H, 8.31; O, 36.65. Found: C, 55.0; H, 8.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.41 (q, Λ, n = 8.0 Hz, 1 H, OC / 7 (Me) COO), 4.38 (q, J _H - h = 7.7 Hz, 1 H, HOCH (Me)), 3.77 (m, J _H -h = 7.8 Hz, 2H, C // ₂ (CH ₂ ) 2 CH ₃ ), 1.54 (d 7 _"H = 7.5 Hz, 3H, OCH (C // ₃₎ COO), 1.39 to 1.32 (m, 2H, CH ₂ C // ₂ CH ₂ CH _3), 1.31 ( d, J _H -H = 7.5 Hz, 3H, HOCH (C / 7 _3)), 1.16 to 1.10 (m, J _H-H = 7.7 Hz, 2H, _{(CH2) 2} C / F _{2 CH3),} 0.85 (t, J _H-H = 7.5 Hz, 3H _{(CH2) 3} C77 _3). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 172.5 (COOBu), 166.3 (C (Me) COO), 73.9 (OC (Me) COOBu), 67.1 (HOC) (Me)), 63.2 (CH ₂ (CH ₂ ) ₂ CH ₃ ), 32.1 (CH ₂ C / ₂ CH ₂ CH ₃ ), 22.2 (OC (CH ₃ ) COO), 19, 2 ((CH ₂ ) ₂ CH ₂ CH ₃ ), 17.2 (HOC (CH ₃ ) COO), 15.7 ((CH ₂ ) ₂ CH ₃ ). GC-MS: m / z = 218.11 for [lactyl-lactate-Bu] ⁺ .

-20EN 306988 B6

Example 46. Preparation of (2S) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and cyclohexan-1-ol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of cyclohexan-1-ol (0.047 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.69 g (6.92 mmol, 91%). Elemental analysis for C 12 H 20 O 5 (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 58.8; H, 8.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.13 (q, J _H- H = Hz ¹ Hz, 1H, OC77 (Me) COO),

4.72 (m, J _H-H = 6.5 Hz, 1H, ClF '), 4.48 (q, J _H-H = 8.3 Hz, 1H, HOCtf (Me)), 3.58- 3.53 (m, 4H, C7 / ₂ ^CHex ), 1.89-1.86 (m, 7H, OCH (C / 73) COO + C // 2 ^CHex ), 1.49 (d, JH-h = 6.9 Hz, 3H, HOCH _(7/3)), 1.31-1.25 (m, 2H, CF ₂ ^{cHex). 13} C NMR (125 MHz, C6D6, 298K): δ 175.5 (COOCHex), 168.2 (C (Me) COO), 74.3 (OC (Me) COOCHex), 67.5 (HOC (Me)) ), 67.4, 31.9, 25.8 (C ^CHex ), 21.0 (OC (CH 3) COO), 17.2 (HOC (CH ₃ ) COO), 15.9 (d ^Hex ).

Example 47. Preparation of (2S) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and cyclohexan-1-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 mL of cyclohexan-1-ol (0.047 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.62 g (6.63 mmol, 87%). Elemental analysis for C ₁₂ H ₂₀ O ₅ (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 58.7; H, 7.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.13 (q, J _H -h = 7.1 Hz, 1H, OCtf (Me) COO),

4.72 (m, J _H-H = 6.5 Hz, 1H, C ¹ H ¹ '), 4.48 (q, J H-H = 8.3 Hz, 1H, HOC77 (Me)), 3.58- 3.53 (m, 4H, Ctf2 ^CHex ), 1.89-1.86 (m, 7H, OCH (Ctf3) COO + ^{Cft CHex} ), 1.49 (d, JH-H = 6.9 Hz, 3H, HOCH ( C7 / 3)), 1.31-1.25 (m, 2H, CH2 ^{cHex). 13} C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 175.5 (COOCHex), 168.2 (C (Me) COO), 74.3 (OC (Me) COOCHex), 69.6 (HOC (Me) ), 67.4, 31.9, 25.8 (C ^Hex ), 21.0 (OC (CH ₃ ) COO), 17.2 (HOC (CH ₃ ) COO), 15.9 (<T ^Hex ).

Example 48. Preparation of (2S) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and cyclohexan-1-ol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of 1-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of cyclohexan-1-ol (0.047 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2A) -2-hydroxypropanoate was 1.66 g (6.79 mmol, 89%). Elemental analysis for C ₁₂ H ₂₀ O ₅ (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 58.6; H, 7.8. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.13 (q, ./ _HH = ^7, 1 Hz, 1H, OCtf (Me) COO)

-21 GB 306988 B6

4.72 (m, J _H-H = 6.5 Hz, 1H, CD ™ '), 4.48 (q, J _{H- H} = 8.3 Hz, 1H, HOC / 7 (Me)), 3 , 58-3,53 (m, 4H, ₂ ^cHex C77), 1.89 to 1.86 (m, 7H, OCH (C773) COO-C / 72 ^CHcx), 1.49 (d, 7H-H = 6 9 Hz, 3H, HOCH (CTD)), 1.31-1.25 (m, 2H, C77 ^cHex _2). ¹³ C NMR (125 MHz, C6D6, 298K): δ 175.5 (COOCHex), 168.2 (C (Me) COO), 74.3 (OC (Me) COOCHex), 69.6 (HOC (Me)) ), 67.4, 31.9, 25.8 (C ° ^ex ), 21.0 (OC (CH 3) COO), 17.2 (HOC (CH ₃ ) COO), 15.9 (d ^Hex ) .

Example 49. Preparation of (2R) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and cyclohexan-1-ol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of cyclohexan-1-ol (0.047 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (R) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2A) -2-hydroxypropanoate was 1.55 g (6.35 mmol, 83%). Elemental analysis of C18 H 20 O 5 (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 58.5; H, 7.7. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.20 (q, J _H -h ⁼ 7.7 Hz, 1H, OC77 (Me) COO),

4.65 (m, J H-H = 7.7 Hz, 1H, C H 2 O), 4.72 (q, 7 _H-H = 8.0 Hz, 1H, HOC H + (Me)), 3, 59-3,54 (m, 4H, ₂ ^cHex C77), 1.97-1.88 (m, 7H, OCH (C773) COO-CH 2 ^cHex), 1.51 (d, JH_ _H = 7.2 Hz, 3H, HOCH (C77 ₃₎₎ 1.30 to 1.22 (m, 2H, C77 ^cHex _2). ¹³ C NMR (125 MHz, C6D6, 298K): δ 171.8 (COOCHex), 165.4 (C (Me) COO), 73.6 (OC (Me) COOCHex), 68.1 (HOC (Me)) ), 65.0 (d ^Hex ), 30.2 (d ^Hex ), 26.6 (d ^Hex ), 21.9 (OC (CH 3) COO), 19.0 (HOC (CH ₃ ) COO), 15 , 7 (d ' ^ex ).

Example 50. Preparation of (2R) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and cyclohexan-1-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 mL of cyclohexan-1-ol (0.047 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 R) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2 R) -2-hydroxypropanoate was 1.58 g (6.47 mmol, 85%). Elemental analysis for C 12 H 20 O 5 (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 58.9; H, 8.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.20 (q, .7 ", = 7.7 Hz, 1H, OCD (Me) COO),

4.65 (m, 7 _H -H = 7.7 Hz, 1H, C77 ^cHex), 4.72 (q, JH-H = 8.0 Hz, 1H, HOCHfMe)), 3.59 to 3.54 (m, 4H, C772 ^cHex), 1.97-1.88 (m, 7H, OCH (C773) COO + CD ₂ ^cHex), 1.51 (d, ./HH = 7.2 Hz, 3H, HOCH ( CTA), 1.30-1.22 (m, 2H, C772 ^CHex ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 171.8 (COOCHex), 165.4 (C (Me) COO), 73.6 (OC (Me) COOCHex), 68.1 (HOC (Me) ), 65.0, 30.2 and 26.6 (d ^Hex ), 21.9 (OC (CH ₃ ) COO), 19.0 (HOC (CH ₃ ) COO), 15.7 (d 6) .

Example 51. Preparation of (2R) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and cyclohexan-1-ol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of cyclohexan-1-ol (0.047 mol) + 0.05 mL of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. Subsequently, all volatile components were evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2R) -1- (cyclohexyloxy) -1-oxopropan-2-yl (2 R) -2-hydroxypropanoate was 1.62 g (6.63 mmol, 87%). Elemental analysis for C ₁₂ H ₂₀ O ₅ (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 59.3; H, 8.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.20 (q, J _H -h = 7.7 Hz, 1H, OCH (Me) COO),

4.65 (m, 7 _H, H = 7.7 Hz, 1H, CH ™ * ^6), 4.72 (q, / HH = 8.0 Hz, 1H, HOCH (Me)), 3,59-3 54 (m, 4H, C / 2 ^CHex ), 1.97-1.88 (m, 7H, OCH (C / 73) COO + C / ₂ ^CHex ), 1.51 (d, 7H-h = 7.2 Hz, 3H, 3H, HOCH (Ctf3)), 1.30-1.22 (m, 2H, Ctf2 ^CHex ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 171.8 (COOCHex), 165.4 (C (Me) COO), 73.6 (OC (Me) COOCHex), 68.1 (HOC (Me) ), 65.0, 30.2 and 26.6 (C ^<Hex ), 21.9 (OC (CH ₃ ) COO), 19.0 (HOC (CH ₃ ) COO), 15.7 (d ^Hex) ).

Example 52. Preparation of 1- (cyclohexyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate rac-lactide and cyclohexan-1-ol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of cyclohexan-1-ol (0.047 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- (cyclohexyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate was 1.57 g (6.43 mmol, 84%). Elemental analysis for C ₁₂ H ₂₀ O ₅ (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 59.3; H,

8.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.18 (q, J _H -h = 6.9 Hz, 1H, OC / f (Me) COO), 4.55 (m, 7 _H- h = 7.0 Hz, 1H, CDCl3 4.42 (q, J _H- h = 7.2 Hz, 1H, HOC / 7 (Me)), 3.55-3.49 (m, 4H, C77 ₍ ^CHex ),

1.99-1.91 (m, 7H, OCH (CTF ₃₎ COO + ₂ -OTf ^cHex), 1.46 (d, JH-H = 7.5 Hz, 3H, HOCH (CTF3)) 1301.25 ( m, 2H, (C / C ( ^hex ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 170.1 (COOCHex), 163.2 (C (Me) COO), 75.1 (OC (Me) COOCHex), 69.4 (HOC (Me) ), 64.8, 32.1, 25.1 (d ^Hex ), 22.2 (OC (CH ₃ ) COO), 19.2 (HOC (CH ₃ ) COO), 15.7 (d ^Hex ) .

Example 53. Preparation of 1- (cyclohexyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and cyclohexan-1-ol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 mL of cyclohexan-1-ol (0.047 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- (cyclohexyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate was 1.67 g (6.84 mmol, 90%). Elemental analysis for C ₁₂ H ₂₀ O ₅ (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 59.2; H,

8.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.18 (q, J _{H- H} = 6.9 Hz 1H, OC / 7 (Me) COO), 4.55 (m, J _{H H)} = 7.0 Hz, 1H, C (OH) ^Hex ), 4.42 (q, _JH-H = 7.2 Hz, 1H, HOCt (Me)), 3.55-3.49 (m, 4H, (Ctf ₂ ^CHex )

1.99-1.91 (m, 7H, OCH (Ct H ₃ ) COO + CH ₂ ^CHex ), 1.46 (d, J H-H = 7.5 Hz, 3H, HOCH (C773)), 1,301.25 ( m, 2H, CH 2 ^Cl 2). ^I3 C NMR (125 MHz, C 6 D _6, 298K): δ 170.1 (COOCHex), 163.2 (C (Me) COO), 75.1 (OC (Me) COOCHex), 69.4 (HOC (Me ), 64.8, 32.1 and 25.1 (d ^Hex ), 22.2 (OC (CH ₃ ) COO), 19.2 (HOC (CH ₃ ) COO), 15.7 (d ^Hex ) .

-23EN 306988 B6

Example 54. Preparation of 1- (cyclohexyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate from L-lactide and cyclohexan-1-ol initiated H1

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of cyclohexan-1-ol (0.047 mol) + 0.05 mL of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- (cyclohexyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate was 1.61 g (6.59 mmol, 86%). Elemental analysis for C ₁₂ H ₂₀ O ₅ (%): C, 59.00; H, 8.15; O, 32.75. Found: C, 59.0; H, 8.0. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.18 (q, 7 _H -H = 6.9 Hz, 1H, O // (Me) COO), 4.55 (m, J H -h = 7.0 Hz, 1H CTI ™ *), 4.42 (q, ./ _H - H = 7.2 Hz, 1H, HOC77 (Me)), 3.55-3.49 (m, 4H, GH ₂ ^CHex )

1.99-1.91 (m, 7H, OCH (C ₇ Z ₃ ) COO + C // ₂ ^CHex ), 1.46 (d, J H-h = 7.5 Hz, 3 H, HOC 7 Z (Me)), 1, 3 ΟΙ, 25 (m, 2H, C H 2 ^-lex ). ¹³ C NMR (125 MHz, _COD, 298K): δ 170.1 (COOCHex), 163.2 (C (Me) COO), 75.1 (OC (Me) COOCHex), 69.4 (HOC (Me ), 64.8, 32.1 and 25.1 (d ^Hex ), 22.2 (OC (CH ₃ ) COO), 19.2 (HOC (CH ₃ ) COO), 15.7 (d ^Hex ) .

Example 55. Preparation of (2S) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and 2-ethyl-hexan-1-ol initiated by HCl

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2X) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2S) -2-hydroxypropanoate was 1.99 g (7.25 mmol, 95%). Elemental Analysis Calcd ₄ H ₂₆ O ₅ (%): C, 61.29; H, 9.55; O, 29.16. Found: C, 61.1; H, 9.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.04 (q, Z _H -h = 7.1 Hz, 1H, OCH (Me) COO),

4.29 (q, Zh-H = 7.0 Hz, 1H, HOCH (Me)), 3.94-3.90 (m, 2H, COOCZ / ^{s _2, líex),} 3.67 (br s, 1H, ZZOC (Me)), 3.47-3.45 (m, 1H, COOCH (TM)), 1.47 (d, H = 7.2 Hz, 3H, CH (C 7 H 3) COO), 1,341.31 (m, 2H, H &lt; + &gt;), 1.24 (d, = 7.1 Hz, 3H, HOC7Z (Me)), 1.13-1.09 (m, 3H, fl &lt; -1 &gt;), 0.870.83 (m, 6H, fl * '), 0.76-0.72 (m, 3H, fl *'). ^I3 C NMR (125 MHz, C 6 D _6, 298K): δ 175.6 (COOEtHex), 171.0 (C (Me) COO), 69.7 (OC (Me) COOEtHex), 67.9 (HOC (Me ), 67.4, 39.4,

30.4, 29.4, 24.2 and 23.6 (C ^{E, Hex} ), 21.0 (OC (CH ₃ ) COO), 17.2 (HOC (CH ₃ ) COO), 14.6 and 11.3 (C ^{, Hex} ). GC-MS: m / z = 274.18 for [lactyl-lactate-EtHex] ⁺ .

Example 56. Preparation of (2S) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and 2-ethyl-hexan-1-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2 S) -2-hydroxypropanoate was 1.97 g (7.18 mmol, 94%). Elemental analysis for C ₁₄ H ₂₆ O _s (%): C, 61.29; H, 9.55; O, 29.16. Found: C, 61.4; H, 9.7. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.04 (q, Z _H -h = 7.1 Hz, 1H, OCfl (Me) COO),

-24EN 306988 B6

4.29 (q, J _H-H = 7.0 Hz, 1H, HOCtf (Me)), 3.94-3.90 (m, 2H, COOCtf ₂ ^ElHex ), 3.67 (br s, 1H, HOC (Me)), 3.47-3.45 (m, 1H, COOCH (TM)), 1.47 (d, JH-h = 7.2 Hz, 3H, CH (CH 3) COO), 1,341.31 (m, 2H, D ™), 1.24 (d, JH-h = 7.1 Hz, 3H, HOCtf (Me)), 1.13-1.09 (m, 3H, [ ^nu ] ^OH ), 0,870,83 (m, 6H, from 0.76 to 0.72 (m, 3H, RR ^{THN). '3} C NMR (125 MHz, C 6 D _6, 298K): δ 175.6 (COOEtHex), 171.0 ( C (Me) (COO), 69.7 (OC (Me) COOE (hex)), 67.9 (HOC (Me)), 67.4, 39.4,

30.4, 29.4, 24.2 and 23.6 (C ^EtHex ), 21.0 (OC (CH ₃ ) COO), 17.2 (HOC (CH ₃ ) COO), 14.6 and 11, 3 (C ^EtHex ). GC-MS: m / z = 274.18 for [lactyl-lactate-EtHex] ⁺ .

Example 57. Preparation of H1-initiated (2S) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and 2-ethyl-hexan-1-ol

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 ml of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2H) -hydroxypropanoate was 1.98 g (7.22 mmol, 95%). Elemental analysis for C ₁₄ H ₂₆ O ₅ (%): C, 61.29; H, 9.55; O, 29.16. Found: C, 61.7; H, 9.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.04 (q, J _H -h = 7.1 Hz, 1H, OCH (Me) COO),

4.29 (q, VH-H = 7.0 Hz, 1H, HOCtf (Me)), 3.94-3.90 (m, 2H, COOC / f ₂ ^EtHex), 3.67 (br s, 1H tFOC (Me)), 3.47-3.45 (m, 1H, COOC / ^4Hex ), 1.47 (d, 7H-h = 7.2 Hz, 3H, CH (Ct 3) COO), 1.341 31 (m, 2H, [nu] ^mex ), 1.24 (d, 7Hh = 7.1 Hz, 3H, HOC (Me)), 1.13-1.09 (m, 3H, [ ^eta ] H) , 0.870.83 (m, 6H, D ™), 0.76-0.72 (m, 3H, [ ^delta] ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.6 (COOEtHex), 171.0 (C (Me) COO), 69.7 (OC (Me) COOEtHex), 67.9 (HOC) (Me)), 67.4, 39.4,

30.4, 29.4, 24.2 and 23.6 (C ^EtHex ), 21.0 (OC (CH ₃ ) COO), 17.2 (HOC (CH ₃ ) COO), 14.6 and 11, 3 (C ^EtHex ). GC-MS: m / z = 274.18 for [L-lactyl-EtHexff.

Example 58. Preparation of (2R) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and 2-ethyl-hexan-1-ol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2R) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2A) -2-hydroxypropanoate was 2.02 g (7.36 mmol, 96%). Elemental analysis for C ₁₄ H ₂₆ O ₅ (%): C, 61.29; H, 9.55; O, 29.16. Found: C, 61.6; H, 9.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.13 (q, J _H -h = 7.2 Hz, 1H, OC 7 / (Me) COO),

4.30 (q, y + - _H = 7.2 Hz, 1H, HOC2 / [Me)), 3.97-3.92 (m, 2H, COOC / C ^EtHex ), 3.52-3.46 (m, 1H, COOCH ™), 1.51 (d, J _H -h = 7.2 Hz, 3H, CH (CD ₃ ) COO), 1.35-1.30 (m, 2H, D ™ 1.27 (d, _{JH H} = 6.8 Hz, 3H, HOCtf (Me)), 1.08-1.02 (m, 3H, 0.82-0.79 (m, 6H, Δ), 0.73-0.70 (m,

3H, 7H ( ^hex ). ¹³ C NMR (125 MHz, C6D6, 298K): δ 174.2 (COOEtHex), 170.7 (C (Me) COO), 68.8 (OC (Me) COOEtHex), 68.0 (HOC (Me)) ), 67.1, 38.2, 30.7, 29.1, 24.2 and 23.5 (C ^EtHex ), 20.7 (OC (CH 3) COO), 17.8 (HOC (CH ₃ )) COO), 13.1 and 11.1 (C ^{E, Hex} ). GC-MS: m / z = 274.18 for [lactyl-lactate-EtHex] ⁺ .

-25GB 306988 B6

Example 59. Preparation of (2R) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and 2-ethylhexan-1-ol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 R) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2 R) -2-hydroxypropanoate was 2.02 g (7.36 mmol, 96%). Elemental analysis for C ₁₄ H ₂₆ O ₅ (%): C, 61.29; H, 9.55; O, 29.16. Found: C, 61.3; Η, 9.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.13 (q, J _H -h = 7.2 Hz, 1Η, OCH (Me) COO),

4.30 (q, 7 _H -H = 7.2 Hz, 1H, HOCD [Me)), 3.97 to 3.92 (m, 2H, COOC // ^W '), 3.52-3.46 (m, 1H, COOC / CH3); 1.51 (d, JH-h = 7.2 Hz, 3H, CH (C7 / 3) COO), 1.35-1.30 (m, 2H, D ™ ^ex ), 1.27 (d, JH _H = 6.8 Hz, 3H, HOCD (Me)), 1.08-1.02 (m, 3H, D ™), 0.82-0, 79 (m, 6H, 0.73-0.70 (m,

3H, # * ""). ¹³ C NMR (125 MHz, C6D6, 298K): δ 174.2 (COOEtHex), 170.7 (C (Me) COO), 68.8 (OC (Me) COOEtHex), 68.0 (HOC (Me)) ), 67.1, 38.2, 30.7, 29.1, 24.2 and 23.5 (C ^EtHex ), 20.7 (OC (CH 3) COO), 17.8 (HOC (CH ₃ )) COO), 13.1 and 11.1 (C ^EtHex ). GC-MS: m / z = 274.18 for [lactyl-lactate-EtHex] ⁺ .

Example 60. Preparation of H1-initiated (2R) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and 2-ethyl-hexan-1-ol

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 ml of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 ml of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2R) -1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl (2 R) -2-hydroxypropanoate was 1.94 g (7.07 mmol, 93%). Elemental analysis for C ₁₄ H ₂₆ O ₅ (%): C, 61.29; H, 9.55; O, 29.16. Found: C, 61.7; H, 9.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.13 (q, J _H -h = 7.2 Hz, 1H, OC77 (Me) COO),

4.30 (q, J _{H -H} = 7.2 Hz, 1H, HOCH (Me)), 3.97-3.92 (m, 2H, COOCD ₂ ^{E, Hex} ), 3.52-3.46 (m, 1H, COOC (d) ^ex ), 1.51 (d, J _H-H = 7.2 Hz, 3H, CH (CD ₃ ) COO), 1.35-1.30 (m, 2H, 1.27 (d, _H = 6.8 Hz, 3H, HOCl (Me)), 1.08-1.02 (m, 3H, 0.82-0.79 (m, 6H, fl ™ '), 0.73-0.70 (m,

3H, 7H). ⁿ C NMR (125 MHz, C6D6, 298K): δ 174.2 (COOEtHex), 170.7 (C (Me) COO), 68.8 (OC (Me) COOEtHex), 68.0 (HOC (Me) ), 67.1, 38.2, 30.7, 29.1, 24.2 and 23.5 (C ^EtHex ), 20.7 (OC (CH 3) COO), 17.8 (HOC (CH ₃ )) COO), 13.1 and 11.1 (C ^EtHex ). GC-MS: m / z = 274.18 for [lactyl-lactate-EtHex] ⁺ .

Example 61. Preparation of 1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl 2-hydroxypropanoate from raclactide and 2-ethyl-hexan-1-ol initiated with HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl 2-hydroxypropanoate was 2.07 g (7.54 mmol, 99%). Elemental analysis for C ₁₄ H ₂₆ O ₅ (%): C, 61.29; H, 9.55; O, 29.16. Found: C, 61.4; H, 9.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.02 (q, J _H -h = 7.1 Hz, 1H, OC77 (Me) COO), 4.31 (q, J _H- H = 7.8 Hz, 1H, HOC77 (Me)), 3.99-3.92 (m, 2H, ₂ COOC77 ^E ® ^ex), 3.52 (br s, 1H, 77OC (Me)), 3 . 45-3.41 (m, 1H, COOCTT ⁶ ®), 1.46 (d, J = 7.8 Hz, 3H, CH (C 773) COO), 1,401.34 (m, 2H, TT ¹² ®), 1.28 (d, JH-h = 6.5 Hz, 3 H, HOC77 (Me)) ), 1.16-1.10 (m, 3H, TT ^Ethex ), 0.940.91 (m, 6H, 0.82-0.77 (m, 3H, TT ¹² ®)) ¹³ C NMR (125 MHz , C ₆ D ₆ , 298 K): δ 172.8

2H, COOCT (f), 3.52 (br s, 1H, = 7.8 Hz, 3H, CH (CTT ₃ ) COO), 1.40 = 6.5 Hz, 3H, HOC77 (Me)) , 1.16-1.10 (m, 3H, TT ^Ethex ), 0.94m, 3H, TT ¹² ®). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 172.8 (COOEtHex), 170.2 (C (Me) COO), 70.1 (OC (Me) COOEtHex), 66.7 (HOC) (Me)), 65.2, 37.3,

32.2, 28.3, 24.1 and 23.9 (C ^E ® ^ex ), 21.2 (OC (CH ₃ ) COO), 17.8 (HOC (CH ₃ ) COO), 14.9 and 10.7 (C ^EtHex ). GC-MS: m / z = 274.18 for [lactyl-lactate-EtHexf.

Example 62. Preparation of 1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl 2-hydroxypropanoate from raclactide and 2-ethylhexan-1-ol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, a solution of 5 ml of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl 2-hydroxypropanoate was 2.05 g (7.47 mmol, 98%). Elemental analysis for C ₁₄ H ₂₆ O ₅ (%): C, 61.29; H, 9.55; O, 29.16. Found: C, 61.3; H, 9.4. 1 HNMR (500 MHz, C ₆ D ₆ , 298K): δ 5.02 (q, δι = 7.1 Hz, 1H, OC77 (Me) COO),

4.31 (q, 7 _H -H = 7.8 Hz, 1H, HOC77 (Me)), 3.99-3.92 (m, 2H, ₂ COOCTT ^Eth "), 3.52 (br s, 1H, TTOC (Me)), 3.45-3.41 (m, 1H, ¹² COOC77 ® "), 1.46 (d, JH-H = 7.8 Hz, 3H, CH (C773) COO) 1401.34 (m, 2H, TT ¹² ® "), 1.28 (d, JH_ _H = 6.5 Hz, 3H, HOC77 (Me)), 1.16 to 1.10 (m, 3H, 77 ™ "), 0.940.91 (m, 6H, TT ¹² ®"), 0.82-0.77 (m, 3H, TT ¹² ® "). ¹³ C NMR (125 MHz, C6D6, 298K): δ 172.8 (COOEtHex), 170.2 (C (Me) COO), 70.1 (OC (Me) COOEtHex), 66.7 (HOC (Me)) ), 65.2, 37.3, 32.2, 28.3, 24.1 and 23.9 (C ^E ® ^ex ), 21.2 (OC (CH 3) COO), 17.8 (HOC (CH ₃ ) COO), 14.9 and 10.7 (C ^E ® ^ex ). GC-MS: m / z = 274.18 for [lactyl-lactate-EtHex] ⁺ .

Example 63. Preparation of HI-initiated 1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl 2-hydroxypropanoate from raclactide and 2-ethyl-hexan-1-ol

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, a solution of 5 mL of 2-ethyl-hexan-1-ol (0.032 mol) + 0.05 mL of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1 - [(2-ethylhexyl) oxy] -1-oxopropan-2-yl 2-hydroxypropanoate was 1.99 g (7.25 mmol,

77 ™, 0.82-0.77 (m, 3H, TT ™). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 172.8 (COOEtHex),

170.2 (C (Me) COO), 70.1 (OC (Me) COOEt Hex), 66.7 (HOC (Me)), 65.2, 37.3, 32.2, 28.3, 24, 1 and 23.9 (C ^E ® ^ex ), 21.2 (OC (CH ₃ ) COO), 17.8 (HOC (CH ₃ ) COO), 14.9 and 10.7 (C ^E ® ^ex ). GC-MS: m / z = 274.18 for [lactyl-lactate-EtHex] ⁺ .

- 77 GB 306988 B6

Example 64. Preparation of (2S) -1-oxo-1-phenoxypropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and phenol initiated by HCl

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HCl (conc. 36%, 0.58 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1-phenoxypropan-2-yl (2S) -2-hydroxypropanoate was 0.48 g (2.01 mmol, 26%). Elemental analysis for C 12 H 145 (%): C, 60.50; H, 5.92; O, 33.58. Found: C, 61.0; H, 6.3. H NMR (500 MHz, C ₆ D <, 298K): δ 7.00 (t, 7 _H -H = 8.0 Hz, 2 H, FF ^H), 6.80 (t, JHH = 7.4 Hz , 1 H, // "), 6.41 (d, JH-H = 8.0 Hz, 2H, Ty ^'1), 4.94 (q, ZH-H = 7.0 Hz, 1H, OC77 (Me ) COO), 4.09 (q, 7 _H -H = 7.0 Hz, 1H, HOCZ / (Me)), 1.33 (d, ./ = _H H ^{6> 7} Hz, ^3H, CH (CH3 (COO), 1.24 (d, 7HH = 7.1Hz, 3H, HOCH (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 177.2 (COOPh), 167.8 (C (Me) COO), 129.2, 124.1 and 113.2 (C ^ph ), 70, 4 (OC (Me) COOPh), 67.7 (HOC (Me)), 20.9 (OC (CH ₃ ) COO), 16.7 (HOC (CH ₃ ) COO).

Example 65. Preparation of (2S) -1-oxo-1-phenoxypropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and phenol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HBr (conc. 48%, 0.44 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1-phenoxypropan-2-yl (2S) -2-hydroxypropanoate was 0.47 g (1.97 mmol, 26%). Elemental analysis of C ₁₂ H ₄ O ₅ (%) : C, 60.50; H, 5.92; O, 33.58. Found: C, 60.4; H, 6.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 7.00 (t, J = 8.0 Hz, 2H, Zf * ¹ ), 6.80 (t, 7H-h = 7 6.4 Hz (1H, 7 / ^h ), 6.41 (d, 1H-h = 8.0 Hz, 2H, 7 / ^h ), 4.94 (q, 7H-h = 7.0 Hz, 1H, OCZZ (Me) COO), 4.09 (q, 7H-h = 7.0Hz, 1H, HOCZ7 (Me)), 1.33 (d, JHh = 6.7Hz, 3H, CH (Ctf3)) COO), 1.24 (d, 7H-h = 7.1Hz, 3H, HCHI). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 177.2 (COOPh), 167.8 (C (Me) COO), 129.2, 124.1 and 113.2 (C ^Ph ), 70, 4 (OC (Me) COOPh), 67.7 (HOC (Me)), 20.9 (OC (CH ₃ ) COO), 16.7 (HOC (CH ₃ ) COO).

Example 66. Preparation of (2S) -1-oxo-1-phenoxypropan-2-yl (2S) -2-hydroxypropanoate from L-lactide and phenol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HI (conc. 67%, 0.51 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2S) -1-oxo-1-phenoxypropan-2-yl (2S) -2-hydroxypropanoate was 0.44 g (1.85 mmol, 24%). Elemental analysis for C ₁₂ H ₄ O ₅ (%): C, 60.50; H, 5.92; O, 33.58. Found: C, 60.3; H, 5.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 7.00 (t, J _H -h = 8.0 Hz, 2H, t ^H ), 6.80 (t, 7 _H -h = 7 , 4 Hz,

(OC (CH ₃₎ COO), 16.7 (HOC (CH ₃₎ COO).

Example 67. Preparation of (2R) -1-oxo-1-phenoxypropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and phenol initiated by HCl

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HCl (conc. 36%, 0.58 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2R) -1-oxo-1-phenoxypropan-2-yl (2H) -2-hydroxypropanoate was 0.40 g (1.68 mmol, 22%). Elemental analysis for C ₁₂ H ₁₀ O ₅ (%): C, 60.50; H, 5.92; O, 33.58. Found: C, 60.4; H,

6.0. * H NMR (500 MHz, C ₆ D _6, 298K) δ 7.09 (t, J _H-H = 7.8 Hz, 2H, Ir ^H), 6.82 (t, JH-H = 7, 2 Hz, 1H, Z / ^11), 6.44 (d, JH-H = 7.5 Hz, 2H, // ^h), 4.98 (q '= 7.0 Hz, 1H, OCZZ (Me COO), 4.22 (q,

7 _H -H = 7.4 Hz, 1H, HOCZZ (Me)), 1.36 (d, J _H -H = 7.0 Hz, 3H, CH (GB7 ₃₎ COO), 1.28 (d, Z = _H = 7.0 Hz, 3H, HOCZ7 (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 177.9 (COOPh), 167.6 (C (Me) COO), 129.2, 124.3, 124.1 and 113.1 ( C ^ph ), 71.0 (OC (Me) COOPh), 67.9 (HOC (Me)), 18.9 (OC (CH ₃ ) COO), 16.2 (HOC (CH ₃ ) COO).

Example 68. Preparation of (2R) -1-oxo-1-phenoxypropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and phenol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene.

The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HBr (conc. 48%, 0.44 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2Z) -1-oxo-1-phenoxypropan-2-yl (2Z) -2-hydroxypropanoate was 0.39 g (1.64 mmol,

%). Elemental analysis for C ₁₂ H ₁₄ O ₅ (%): C, 60.50; H, 5.92; O, 33.58. Found: C, 60.0; H,

7.0 Hz, 3H, HOC 2 Z (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 177.9 (COOPh), 167.6 (C (Me) COO), 129.2, 124.3, 124.1 and 113.1 ( C ^Ph), 71.0 (OC (Me) COOPh), 67.9 (HOC (Me)), 18.9 (OC (CH ₃₎ COO), 16.2 (HOC (CH ₃₎ COO).

Example 69. Preparation of (2R) -1-oxo-1-phenoxypropan-2-yl (2R) -2-hydroxypropanoate from D-lactide and phenol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HI (conc. 67%, 0.51 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure

folders. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of (2 R) -1-oxo-1-phenoxypropan-2-yl (2 R) -2-hydroxypropanoate was 0.45 g (1.89 mmol, 25%). Elemental analysis for C 12 H 14 O 5 (%): C, 60.50; H, 5.92; O, 33.58. Found: C, 61.2; H, 6.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 7.09 (t, J f = 7.8 Hz, 2H, f P '), 6.82 (t, J _{H- H} = 7.2 Hz, 1H, 7 / ^H), 6.44 (d, JH-H = 7.5 Hz, 2H, LP ^H), 4.98 (q, JH-H = 7.0 Hz, 1H, OCH (Me (COO), 4.22 (q, J _H-H = 7.4 Hz, 1H, HOC H (Me)), 1.36 (d, -111-11 = 7.0 Hz, 3H, CH (C) / 7 ₃₎ COO), 1.28 (d, J _H -H = 7.0 Hz, 3H, HOC / 7 (Me)). ¹³ C NMR (125 MHz, C6D6, 298K): δ 177.9 (COOPh), 167.6 (C (Me) COO), 129.2, 124.3, 124.1, and 113.1 (C ^ph ) , 71.0 (OC (Me) COOPh), 67.9 (HOC (Me)), 18.9 (OC (CH 3) COO), 16.2 (HOC (CH ₃ ) COO).

Example 70. Preparation of 1-oxo-1-phenoxypropan-2-yl 2-hydroxypropanoate from rac-lactide and phenol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HCl (conc. 36%, 0.58 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-oxo-1-phenoxypropan-2-yl 2-hydroxypropanoate was 0.47 g (1.97 mmol, 26%). Elemental analysis for C ₁₂ H ₁₄ O ₅ (%): C, 60.50; H, 5.92; O, 33.58. Found: C, 60.4; H, 6.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 7.08 (t, J _H -h = 8.0 Hz, 2H, iPj, 6.84 (t, J _H -h = 7.5 Hz, 1H, [beta]), 6.71 (d, JH-h = 7.5 Hz, 2H, [beta] ^H ), 4.79 (q, _JH- h = 7.2 Hz, 1H, OCH (Me)) COO), 4.20 (q, J _H -h =

7.5 Hz, 1H, HOCt (Me)), 1.38 (d, J _H-H = 7.2 Hz, 3H, CH (CH ₃ ) COO), 1.30 (d, J _H-H = 7.0 Hz, 3H, HOCt (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.6 (COOPh), 166.7 (C (Me) COO), 129.1,

122.2, 113.5 (C ^Ph), 71.1 (OC (Me) COOPh), 65.2 (HOC (Me)), 19.2 (OC (CH ₃₎ COO), 15.3 (HOC (CH ₃ ) COO).

Example 71. Preparation of 1-oxo-1-phenoxypropan-2-yl 2-hydroxypropanoate from rac-lactide and phenol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HBr (conc. 48%, 0.44 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-oxo-1-phenoxypropan-2-yl 2-hydroxypropanoate was 0.48 g (2.01 mmol, 26%). Elemental analysis for C ₁₂ H ₁₄ O ₅ (%): C, 60.50; H, 5.92; O, 33.58. Found: C, 60.5; H, 6.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 7.08 (t, J _H -h = 8.0 Hz, 2H, f P'j, 6.84 (t, J _HH = 7.5 Hz) 1 H, fp), 6.71 (d, J H-H = 7.5 Hz, 2H, iPj, 4.79 (q, _JH-H = 7.2 Hz, 1H, OC77 (Me) COO)) 4.20 (q, J _{H- H} =

7.5 Hz, 1H, HOC / R (Me)), 1.38 (d, 7 _{Η -η} = 7.2 Hz, 3H, CH (C / 7 ₃₎ COO), 1.30 (d, 7 _H-H = 7.0 Hz, 3H, HOCH (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.6 (COOPh), 166.7 (C (Me) COO), 129.1,

122.2 and 113.5 (C ^ph ), 71.1 (OC (Me) COOPh), 65.2 (HOC (Me)), 19.2 (OC (CH ₃ ) COO), 15.3 (HOC) (CH ₃ ) COO).

-30GB 306988 B6

Example 72. Preparation of 1-oxo-1-phenoxypropan-2-yl 2-hydroxypropanoate from HI-initiated rac-lactide and phenol

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 2.82 g of phenol (0.030 mol) and 0.05 ml of HI (conc. 67%, 0.51 mmol) were added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1-oxo-1-phenoxypropan-2-yl 2-hydroxypropanoate was 0.45 g (1.89 mmol, 25%). Elemental analysis for C 12 H 14 O 5 (%): C, 60.50; H, 5.92; O, 33.58. Found: C, 60.6; H, 6.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 7.08 (t, Z _H -h = 8.0 Hz, 2H, 1 H), 6.84 (t, Z _H -h = 7.5 Hz, 1 H, FF ^H), 6.71 (d, Jh_h = 7.5 Hz, 2H, // ^h), 4.79 (q, ZH-H = 7.2 Hz, 1H, OC (Z (Me) COO), 4.20 (q, VH =

7.5 Hz, 1H, HOC 7 Z (Me)), 1.38 (d, 7 _H h = 7.2 Hz, 3H, CH (C ₇ Z ₃ ) COO), 1.30 (d, J _H -h = 7 0 Hz, 3H, HOCt (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 176.6 (COOPh), 166.7 (C (Me) COO), 129.1,

122.2 and 113.5 (C ^ph ), 71.1 (OC (Me) COOPh), 65.2 (HOC (Me)), 19.2 (OC (CH ₃ ) COO), 15.3 (HOC) (CH ₃ ) COO).

Example 73. Preparation of butane-1,4-diylbis (oxy (2S, 2'S) -1-oxopropane-1,2-diyl) (2S, 2'S) -bis (2-hydroxypropanoate) from L-lactide and butane-1,4- diol initiated by IIC1

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of butane-1,4-diylbis (oxy (2 ', 2')) -1-oxopropane-1,2-diyl) (2A, 2'S ') bis (2-hydroxypropanoate) was 1.50 g. (3.96 mmol, 52%). Elemental Analysis C ₆ H _{26 0} Oi (%): C, 50.79; H, 6.93; O,

42.28. Found: C, 50.9; H, 7.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.06 (q, J _H -h = 7.1 Hz, 2H, OCZ 7 (Me) COO), 4.29 (q, 7 _H - h = 6.9 Hz, 2H, HOC 2 F (Me)), 4.14-4.10 (m, 4H, COOC ₇ Z ₂ ^Bu ),

1.69-1.63 (m, 2H, 1.59-1.51 (m, 2H, / Λ), 1.46 (d, 7 _H -H = 7.1 Hz, 6H, CH (GB7 ₃ (COO), 1.41 (d, ./".[!= 7.0 Hz, 6H, HOC 7 Z (Me)) ¹³ C NMR (125 MHz, C6D6, 298K): δ 175.0 (COOBu), 170.8 (C (Me) COO), 69.3 (OC (Me) COOBu), 66.7 (HOC (Me)), 65.5 (OCH, (CH 2) 3 O), 61.7 (O ( CH 2 (3CH 2 O), 28.7 (C ^Bu ), 25.0 (OC (CH 3) COO), 20.3 (HOC (CH ₃ ) COO), 16.9 (C ^Bu ).

Example 74. Preparation of butane-1,4-diylbis (oxy (2S, 2'S) -1-oxopropane-1,2-diyl) (2S, 2'S) -bis (2-hydroxypropanoate) from L-lactide and butane-1,4- diol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of butane-1,4-diylbis (oxy (25,2,5) -1-oxopropane-1,2-diyl) (2,2 ', S-bis (2-hydroxypropanoate)) was 1.59 g (4.20 mmol). , 55%). Elemental analysis C ₆ H _{26 0} Oi (%): C, 50.79; H, 6.93; O,

42.28. Found: C, 50.9; H, 7.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.06 (q, J _{H- H} = 7.1 Hz, 2H, OCH (Me) COO), 4.29 (q, = 6, 9 Hz, 2H, HOCH (Me)), 4.14-4.10 (m, 4H, COOCH ₂ ^Bu ),

1.69-1.63 (m, 2H, Z / ⁶ '), 1.59-1.51 (m, 2H, Zn ¹¹ ), 1.46 (d, J _H -h = 7.1 Hz, 6H, CH (C ₇ Z ₃ ) COO), 1.41. 51 (d, J _H-H = 7.0 Hz, 6H, HOC 7 L (Me)). ⁿ C NMR (125 MHz, C6D6, 298K): δ 175.0 (COOBu), 170.8 (C (Me) COO), 69.3 (OC (Me) COOBu), 66.7 (HOC (Me) ), 65.5 (OCH 2 (CH 2) 3 O), 61.7 (O (CH 2) 3 CH 2 O), 28.7 (C ^Bu ), 25.0 (OC (CH 3) COO), 20.3 (HOC (CH) ₃ ) COO), 16.9 (C ^Bu ).

Example 75. Preparation of butane-1,4-diylbis (oxy (2S, 2'S) -1-oxopropane-1,2-diyl) (2S, 2'S) -bis (2-hydroxypropanoate) from L-lactide and butane-1,4- diol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of L-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of butane-1,4-diyl bis (oxy (25 ', 2'.S ¹⁾ - 1-oxopropan-l, 2-diyl) (25,2'5) -bis (2-hydroxypropanoate) was 1.55 g (4.10 mmol, 54%). Elemental Analysis C ₆ H _{26 0} Oi (%): C, 50.79; H, 6.93; O,

42.28. Found: C, 50.9; Η, 7.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.06 (q, J _H -h = Hz, 2H, OC / L (Me) COO), 4.29 (q, L _H -h) = 6.9 Hz, 2Η, HOC7L (Me)), 4.14-4.10 (m, 4Η, COOCD ₂ ^Bu ),

1.69-1.63 (m, 2H, D ^Bu ), 1.59-1.51 (m, 2H, L / ⁸ "), 1.46 (d, J / H = 7.1 Hz, 6H) CH (C7L3) (COO), 1.41 (d, LH-H = 7.0 Hz, 6H, HOC7L (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 175.0 (COOBu), 170.8 (C (Me) COO), 69.3 (OC (Me) COOBu), 66.7 (HOC (Me) ), 65.5 (OCH ₂ (CH ₂ ) ₃ O), 61.7 (O (CH ₂ ) ₃ CH ₂ O), 28.7 (C ^Bu ), 25.0 (OC (CH ₃ ) COO) ), 20.3 (HOC (CH ₃ ) COO), 16.9 (C ^Bu ).

Example 76. Preparation of butane-1,4-diylbis (oxy (2R, 2'R) -1-oxopropane-1,2-diyl) (2R, 2'R) -bis (2-hydroxypropanoate) from D-lactide and butane- Of 1,4-diol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of butane-1,4-diylbis (oxy (2L ', 2'L') -1-oxopropane-1,2-diyl) (2 S, 2 S) -bis (2-hydroxypropanoate) was 1.60 g ( 4.22 mmol, 55%). Elemental analysis for C 16 H ₂₆ O ₁₀ (%): C, 50.79; H, 6.93; O,

42.28. Found: C, 50.9; H, 7.3. ¹ H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, _1H -h = 7.0 Hz, 2H, OCH (Me) COO), 4.25 (q, J _H- h = 7.0 Hz, 2H, HOC / L (Me)), 4.15M, 10 (m, 4H, COOC ₇ L ₂ ^Bu ),

1.71-1.66 (m, 2H, D ⁸ "), 1.58-1.51 (m, 2H, L / ⁸ "), 1.38 (d, ./H "= 7.5 Hz) 6H, CH (CL / 3) COO), 1.44 (d, J H-H = 7.5 Hz, 6H, HOCL7 (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 175.2 (COOBu), 169.7 (C (Me) COO), 69.2 (OC (Me) COOBu), 66.9 (HOC (Me) ), 64.3 (OCH ₂ (CH ₂ ) ₃ O), 61.8 (O (CH ₂ ) ₃ CH ₂ O), 27.9 (C ^Bu ), 25.1 (OC (CH ₃ ) COO 19.3 (HOC (CH ₃ ) COO), 15.3 (C ^BH ).

Example 77. Preparation of butane-1,4-diylbis (oxy (2R, 2'R) -1-oxopropane-1,2-diyl) (2R, 2'R) -bis (2-hydroxypropanoate) from D-lactide and butane- Of the 1,4-diol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

-32GB 306988 B6

The yield of butane-1,4-diylbis (oxy (2 R, 2 R) -1-oxopropane-1,2-diyl) (2 R, 2 ', 7 R) -bis (2-hydroxypropanoate) was 1.48 g ( 3.91 mmol, 51%). Elemental analysis% (%): C, 50.79; H, 6.93; O,

42.28. Found: C, 50.5; H, 6.7. * H NMR (500 MHz, C ₆ D _6, 298K) δ 5.05 (q, 7 _{H. H} = 7.0 Hz, 2H, OC7Z (Me) COO), 4.25 (q, 7 _H _ _H = 7.0 Hz, 2H, HOC 7 Z (Me)), 4.15 → 1.10 (m, 4H, COOC ₇ Z ₂ ^Bu ),

1.71-1.66 (m, 2H, Z / ⁸ "), 1.58-1.51 (m, 2H, Z / ⁸ "), 1.38 (d, 7H_H = 7.5Hz, 6H) CH (CZZ) COO), 1.44 (d, 1H-h = 7.5 Hz, 6H, HOCZ7 (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 175.2 (COOBu), 169.7 (C (Me) COO), 69.2 (OC (Me) COOBu), 66.9 (HOC (Me) ), 64.3 (OCH ₂ (CH ₂ ) ₃ O), 61.8 (O (CH ₂ ) ₃ CH ₂ O), 27.9 (C ^Bu ), 25.1 (OC (CH ₃ ) COO 19.3 (HOC (CH ₃ ) COO), 15.3 (C ^Bu ).

Example 78. Preparation of butane-1,4-diylbis (oxy (2R, 2'R) -1-oxopropane-1,2-diyl) (2R, 2'R) -bis (2-hydroxypropanoate) from D-lactide and butane- of 1,4-diol initiated by H1

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of butane-1,4-diylbis (oxy (2R, 2R) -1-oxopropane-1,2-diyl) (2R, 2'7R) -bis (2-hydroxypropanoate) was 1.49 g (3). , 94 mmol, 52%). Elemental analysis for C ₁₆ H ₂₆ O 10 (%): C, 50.79; H, 6.93; O,

42.28. Found: C, 50.6; H, 6.8. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, 7, J = 7.0 Hz, 2H, OCZ 7 (Me) COO), 4.25 (q, Z _H) -h = 7.0 Hz, 2H, HOCZ7 (Me)), 4.15-4.10 (m, 4H, COOCZ7 ₂ ^Bu ),

1.71-1.66 (m, 2H, Z / ⁸ '), 1.58-1.51 (m, 2H, Z / ⁸ '), 1.38 (d, 7 ',, = 7, 5 Hz, 6H, CH (CZ 2) COO), 1.44 (d, 7h-h = 7.5 Hz, 6H, HOC / Z (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 175.2 (COOBu), 169.7 (C (Me) COO), 69.2 (OC (Me) COOBu), 66.9 (HOC (Me) ), 64.3 (OCH ₂ (CH ₂ ) ₃ O), 61.8 (O (CH ₂ ) ₃ CH ₂ O), 27.9 (C ^Bu ), 25.1 (OC (CH ₃ ) COO 19.3 (HOC (CH ₃ ) COO), 15.3 (C ^Bu ).

Example 79. Preparation of butane-1,4-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and butane-1,4-diol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of butane-1,4-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.52 g (4.02 mmol, 53%). Elemental analysis for C ₁₆ H ₂₆ O ₁₀ (%): C, 50.79; H, 6.93; O, 42.28. Found: C, 50.7; H, 6.8. * H NMR (500 MHz, C ₆ D _6, 298K) δ 5.06 (q, 7 _H _ _H = 7.0 Hz, 2H, OC7Z (Me) COO)

4.35 (q, _H 7 _h = 7.5 Hz, 2H, HOCZ7 (Me)), 4.2 W, 14 (m, 4 H, COOC / 7 ₂ ^Bu), 1.68-1.63 (m , 2H, Z / ⁸ ")

1.54-1.44 (m, 2H, Z / ⁸ ), 1.36 (d, 7H.H = 7.0 Hz, 6H, CH (C7Z3) COO), 1.40 (d, 7H_H = 7 2 Hz, 6H, HOCZ7 (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 174.4 (COOBu), 169.8 (C (Me) COO), 69.0 (OC (Me) COOBu), 66.7 (HOC (Me) ), 64.2 (OCH ₂ (CH ₂ ) ₃ O), 61.1 (O (CH ₂ ) ₃ CH ₂ O), 26.2 (C ^Bu ), 24.3 (OC (CH ₃ ) COO) 19.1 (HOC (CH ₃ ) COO), 15.8 (C ^Bu ).

1 * 2

Example 80. Preparation of HBr initiated butane-1,4-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and butane-1,4-diol

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of butane-1,4-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.52 g (4.02 mmol, 53%). Elemental Analysis C ₆ H 6 O _{2, 0} (%): C, 50.79; H, 6.93; O, 42.28. Found: C, 50.6; H, 6.9. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.06 (q, 7.0 Hz, 2H, OC // (Me) COO),

4.35 (q, 7 _H -H = 7.5 Hz, 2H, HOCtf (Me)), 4.21 ^ 1.14 (m, 4H, COOCH ₂ ^Bu), 1.68-1.63 (m , 2H, Ti ⁰ "),

1.54-1.44 (m, 2H, H ⁶ '), 1.36 (d, 7Η-η = 7.0 Hz, 6H, CH (C 7/3) COO), 1.40 (d, JH-h = 7.2 Hz, 6H, HOCt (Me)). ^I3 C NMR (125 MHz, C 6 D _6, 298K): δ 174.4 (COOBu), 169.8 (C (Me) COO), 69.0 (OC (Me) COOBu), 66.7 (HOC (Me ), 64.2 (OCH ₂ (CH ₂ ) ₃ O), 61.1 (O (CH ₂ ) ₃ CH ₂ O), 26.2 (C ^Bu ), 24.3 (OC (CH ₃ ) COO) 19.1 (HOC (CH ₃ ) COO), 15.8 (C ^Bu ).

Example 81. Preparation of butane-1,4-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and butane-1,4-diol initiated by HI

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of butane-1,4-diol (0.056 mol) + 0.05 mL of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of butane-1,4-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.58 g (4.17 mmol, 55%). Elemental analysis for C 10 H 10 O 10 (%): C, 50.79; H, 6.93; O, 42.28. Found: C, 50.9; H, 6.7. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.06 (q, = 7.0 Hz, 2H, OCtf (Me) COO),

4.35 (q, J _H-H = 7.5 Hz, 2H, HOC 7 / (Me)), 4.21-4.14 (m, 4H, COOCt ₂ ^Bu ), 1.68-1.63 ( m, 2H, / 7 °)

1.54-1.44 ( _m , 2H, Z / ⁸ & apos ^; ), 1.36 (d, JH-h = 7.0 Hz, 6H, CH (CH3) COO), 1.40 (d, JH) -h = 7.2 Hz, 6H, HOCt (Me)). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 174.4 (COOBu), 169.8 (C (Me) COO), 69.0 (OC (Me) COOBu), 66.7 (HOC (Me) ), 64.2 (OCH ₂ (CH ₂ ) ₃ O), 61.1 (O (CH ₂ ) ₃ CH ₂ O), 26.2 (C ^Bu ), 24.3 (OC (CH ₃ ) COO) 19.1 (HOC (CH ₃ ) COO), 15.8 (C ^Bu ).

Example 82. Preparation of pentane-1,5-diylbis (oxy (2S ', 2'5) -1-oxopropane-1,2-diyl) (2S, 2' »S ') bis (2-hydroxypropanoate) from L-lactide and pentane-1,5-diol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of C-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. Subsequently, all volatile constituents were evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diyl bis (oxy (25,2'5) -l-oxopropan-l, 2-diyl) (25 ', 2', ^T S) -bis (2-hydroxypropanoate) was 1.60 g (4.08 mmol, 53%). Elemental analysis for C ₁₇ H ₂₈ O 10 (%): C, 50.03; H, 7.19; O,

40.77. Found: C, 50.1; H, 7.3. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.09 (q, 7 _H -H = 7.1 Hz, 2H, 0C7 / (Me) C00), 4.31 (q, ./ = 6.9 Hz, 2H, HOCt (Me), 3.99-3.93 (m, 4H, COOC7 / ^ent ),

1.49 (d, ./ _"H = 6.9 Hz, 6H, CH (CPA) COO), 1.40-1.35 (m, 2H, IF ^ENT), 1.32-1.26 (m , 8H,

-34GB 306988 B6

HOC / 7 (Me) and 1 H (tm), 1.10-1.04 (m, 2H, t ' ^ent ). ¹³ C NMR (125 MHz, C6D6, 298K): δ 175.1 (COOPent), 170.8 (C (Me) COO), 69.4 (OC (Me) COOPent), 66.9 (HOC (Me)) ), 65.5 (OCH 2 (CH 2) 4 O), 62.3 (O (CH 2) 4 CH 2 O), 32.1 and 28.7 (C ^Pent ), 22.1 (OC (CH 3) COO), 20.5 (HOC (CH ₃₎ COO), 17.0 (C ^Pent).

Example 83. Preparation of pentane-1,5-dimethylbis (oxy (25,2'S) -1-oxopropane-1,2-diyl) (2/7277) bis (2-hydroxypropanoate) from L-lactide and pentane-1, Of 5-diol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diylbis (oxy (25 ', 2777) -1-oxopropane-1,2-diyl) (2.S', 277) bis (2-hydroxypropanoate) was 1.65 g (4). , 20 mmol, 55%). Elemental analysis for C ₁₇ H ₂₈ O ₁₀ (%): C, 50.03; H, 7.19; O,

40.77. Found: C, 50.0; H, 7.3. ¹ H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.09 (q, J _H -h = 7.1 Hz, 2H, OC77 (Me) COO), 4.31 (q, J _H- h = 6.9 Hz, 2H, HOC7 / (Me)), 3.99-3.93 (m, 4H, COOC // ₂ ^Pent ),

1.49 (d, JH-H = 6.9 Hz, 6H, CH (C77 ₃₎ COO), 1.40-1.35 (m, 2H, LF ^EAT) "1.32-1.26 (m , 8H, HOC 7 / (Me) and 1 H ™ 1,10-1,04 (m, 2H, 1 H ™). ¹³ C NMR (125 MHz, C6D6, 298K): δ 175.1 (COOPent), 170.8 (C (Me) COO), 69.4 (OC (Me) COOPent), 66.9 (HOC (Me)) ), 65.5 (OCH 2 (CH 2) 4 O), 62.3 (O (CH 2) 4 CH 2 O), 32.1 and 28.7 (C ^Pent ), 22.1 (OC (CH 3) COO), 20.5 (HOC (CH ₃₎ COO), 17.0 (C ^Pent).

Example 84. Preparation of pentane-1,5-diylbis (oxy (2S, 277) -1-oxopropane-1,2-diyl) (2S, 277) -bis (2-hydroxypropanoate) from L-lactide and pentane-1,5- hole initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diylbis (oxy (2A, 2777) -1-oxopropane-1,2-diyl) (2S, 277) bis (2-hydroxypropanoate) was 1.68 g (4.28 mmol), 56%). Elemental analysis for C 11 H 15 N 3 O 4 (%): C, 50.03; H, 7.19; O,

40.77. Found: C, 49.9; H, 7.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.09 (q, J _H -h = 7.1 Hz, 2H, OC77 (Me) COO), 4.31 (q, J _H- h = 6.9 Hz, 2H, HOCt (Me)), 3.99-3.93 (m, 4H, COOC // ₂ ^Pent ),

1.49 (d, J _{H- H} = 6.9 Hz, 6H, CH (CH ₃ ) COO), 1.40-1.35 (m, 2H, 1H), 1.32-1.26 ( m, 8H, HOC77 (Me) and 1f ™), 1.10-1.04 (m, 2H, 1f ™). ¹³ C NMR (125 MHz, C6D6, 298K): δ 175.1 (COOPent), 170.8 (C (Me) COO), 69.4 (OC (Me) COOPent), 66.9 (HOC (Me)) ), 65.5 (OCH 2 (CH 2) 4 O), 62.3 (O (CH 2) 4 CH 2 O), 32.1 and 28.7 (C ^Pent ), 22.1 (OC (CH 3) COO), 20.5 (HOC (CH ₃₎ COO), 17.0 (C ^Pent).

Example 85. Preparation of pentane-1,5-diylbis (oxy (2?, 2? 7?) -1-oxopropane-1,2-diyl) (2?, 2? 7?) - bis (2-hydroxypropanoate) from D-lactide and HCl-initiated pentane-1,5-diol

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. Subsequently, all were evaporated under reduced pressure

volatile components and the obtained residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diyibis (oxy (2 R, 2 R) -1-oxopropane-1,2-diyl) (2 R, 2 R) -bis (2-hydroxypropanoate) was 1.69 g (4%). , 31 mmol, 56%). Elemental analysis for C 11 H 10 O 10 (%): C, 50.03; H, 7.19; O, 40.77. Found: C, 50.0; H, 7.1. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.12 (q, J _"H = 7.0 Hz, 2H, oc7 / (Me) COO), 4.23 (q, ./ _HH ⁼ 7.2 Hz, 2H, HOCD (Me)), 4.05-3.95 (m, 4H, COOCD2 ^Pent ), 1.52 (d, JH-h = 7.0 Hz, 6H, CH (CD) ₃ ) COO), 1.49-1.44 (m, 2H, t '), 1.40-1.32 (m, 8H,

HOCD (Me) 1.09-1.05 (m, 2H, D of ^Pent ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298K): δ 175.4 (COOPent), 170.5 (C (Me) COO), 69.3 (OC (Me) COOPent), 66.2 (HOC) (Me)), 64.8 (OCH ₂ (CH ₂ ) ₄ O), 62.5 (O (CH ₂ ) ₄ CH ₂ O), 31.6 and 27.7 (C ^Pent ), 22.1 ( OC (CH ₃ ) COO), 20.2 (HOC (CH ₃ ) COO), 16.8 (C ^Pent ).

Example 86. Preparation of pentane-1,5-diylbis (oxy (2R, 2'7R) -1-oxopropane-1,2-diyl) (2R, 2'R) -bis (2-hydroxypropanoate) from D- lactide and pentane-1,5-diol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diylbis (oxy (2 R, 2 R) -1-oxopropane-1,2-diyl) (2 R, 2 R) -bis (2-hydroxypropanoate) was 1.72g (4.38) mmol, 57%). Elemental analysis for C 11 H 11 O 3 (%): C, 50.03; H, 7.19; O,

40.77. Found: C, 50.1; H, 7.3. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.12 (q, 7 _H _ _H = 7.0 Hz,

(COOPent), 170.5 (C (Me) COO), 69.3 (OC (Me) COOPent), 66.2 (HOC (Me)), 64.8 (OCH ₂ (CH ₂ ) ₄ O), 62.5 (O (CH ₂ ) ₄ CH ₂ O), 31.6 and 27.7 (C ^Pent ), 22.1 (OC (CH ₃ ) COO), 20.2 (HOC (CH ₃ ) COO) , 16.8 (C ^Pen ').

Example 87. Preparation of pentane-1,5-diylbis (oxy (2 R, 2 R) -1-oxopropane-1,2-diyl) (2 R, 2 R) -bis (2-hydroxypropanoate) from D-lactide and pentane- Of 1,5-diol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of HI (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diylbis (oxy (2 R, 2 R, 1 R-1-oxopropane-1,2-diyl) (2 R, 2 ', 7 R) -bis (2-hydroxypropanoate) was 1.62 g ( 4.13 mmol, 54%) Elemental analysis for CpH ^OioO (%): C, 50.03; H, 7.19;

40.77. Found: C, 50.2; H, 7.4. ^! H NMR (500 MHz, C ₆ D _6, 298K) δ 5.12 (q, J _H n = 7.0 Hz, 2H, OCtf (Me) COO), 4.23 (q, J _HH = 7, 2 Hz, 2H, HOCD (Me)), 4.05-3.95 (m, 4H, COOC7 / ₂ ^Pcnt ),

HOC 7 ((Me) and H +), 1.09-1.05 (m, 2H, m +). ¹³ C NMR (125 MHz, C6D6, 298K): δ 175.4 (COOPent), 170.5 (C (Me) COO), 69.3 (OC (Me) COOPent), 66.2 (HOC (Me)) ), 64.8 (OCH 2 (CH 2) 4 O), 62.5 (O (CH 2) 4 CH 2 O), 31.6 and 27.7 (C ^Pent ), 22.1 (OC (CH 3) COO), 20.2 (HOC _(CH3) COO), 16.8 (C ^Pent).

-36GB 306988 B6

Example 88. Preparation of HCl initiated pentane-1,5-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and pentane-1,5-diol

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.67 g (4.25 mmol, 56%). Elemental analysis for C ₁₇ H ₂₈ O ₁₀ (%): C, 50.03; H, 7.19; O, 40.77. Found: C, 50.5; H, 7.5. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.11 (q, J _H = 7.2 Hz, 2H, OCtf (Me) COO),

4.20 (q, 7h-h = 7.2Hz, 2H, HOC77 (Me)), 4.05-3.96 (m, 4H, COOC / ₂ ^Pent ), 1.54 (d, JH-); h = 7.0 Hz, 6H, CH (CH 3) COO), 1.48-1.43 (m, 2H, if ^ent ), 1.40-1.33 (m, 8H, HOC // (Me) and Rf ^EAI), 1.29-1.24 (m, 2H, H + ^{ENT). I3} C NMR (125 MHz, C 6 D _6, 298K): δ 174.6 (COOPent), 170.1 (C (Me) COO), 70.0 (OC (Me) COOPent), 66.4 (HOC (Me ), 64.1 (OCH ₂ (CH ₂ ) ₄₀ ), 62.3 (O (CH ₂ ) ₄ CH ₂ O), 31.6 and 27.2 (C ^Pent ), 22.1 (OC ( CH ₃ ) COO), 20.5 (HOC (CH ₃ ) COO), 16.1 (C ^Pent ).

Example 89. Preparation of pentane-1,5-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and pentane-1,5-diol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of HBr (conc. 48%, 0.44 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.66 g (4.23 mmol, 55%). Elemental analysis C ₁₇ H ₂₈ 0q (%): C, 50.03; H, 7.19; O, 40.77. Found: C, 50.0; H, 7.1. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.11 (q, 7, _JHH ⁼ 7.2 Hz, 2H, OC77 (Me) COO)

4.20 (q, J _H-H = 7.2 Hz, 2H, HOCtf (Me)), 4.05-3.96 (m, 4H, COOCff ™), 1.54 (d, 7 _{Η -η} = 7.0 Hz, 6H, CH _(CH3) COO), 1.48-1.43 (m, 2H, 1.40-1.33 (m, 8H, // HOC (Me) // and ^ent ), 1.29-1.24 (m, 2H, H ^{Pent). 13} C NMR (125 MHz, C6D6, 298K): δ 174.6 (COOPent), 170.1 (C (Me) COO), 70 , 0 (OC (Me) COOPent), 66.4 (HOC (Me)), 64.1 (OCH 2 (CH 2) 4 O), 62.3 (O (CH 2) 4 CH 2 O), 31.6 and 27.2 ( C ^Pent ), 22.1 (OC (CH 3) COO), 20.5 (HOC (CH ₃ ) COO), 16.1 (C ^Pent ).

Example 90. Preparation of H1-initiated pentane-1,5-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and pentane-1,5-diol

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 5 mL of pentane-1,5-diol (0.047 mol) + 0.05 mL of H1 (conc. 67%, 0.51 mmol) was added, and the resulting reaction mixture was stirred for an additional 10 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of pentane-1,5-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.67 g (4.26 mmol, 56%). Elemental analysis for C ₁₇ H ₂₈ O ₁₀ (%): C, 50.03; H, 7.19; O, 40.77. Found: C, 49.9; H, 7.0. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.11 (q, J _H -h = 7.2 Hz, 2H, OC77 (Me) COO), δ 77

4.20 (q, J _H-H = 7.2 Hz, 2H, HOCZZ (Me)), 4.05-3.96 (m, 4H, COOCZ ₂ ^Pent ), 1.54 (d, 2H) = 7.0 Hz, 6H, CH (CZZ 3) COO), 1.48-1.43 (m, 2H, H +), 1.40-1.33 (m, 8H, HOCZZ (Me) and Z) / ^en '), 1.29-1.24 (m, 2H, ^en ff j. ¹³ C NMR (125 MHz, C 6 D _6, 298K): δ 174.6 (COOPent), 170.1 (C (Me) COO), 70.0 (OC (Me) COOPent), 66.4 (HOC (Me)), 64.1 (OCH ₂ (CH ₂ ) ₄ O), 62.3 (O (CH ₂ ) ₄ CH ₂₎ O), 31.6 and 27.2 (C ^Pent ), 22.1 (OC (CH ₃ ) COO), 20.5 (HOC (CH ₃ ) COO), 16.1 (C ^Pent ).

Example 91. Preparation of hexane-1,6-diylbis (oxy (2?, 2 '5) -1-oxopropane-1,2-diyl) (2S, 2'S) -bis (2-hydroxypropanoate) from L-lactide and hexane-1, Of 6-diol initiated with HCl

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diyl LBIS (oxy (2 ₁ S, 2'S) -l-oxopropan-1,2-diyl) (25.2 ', S') - bis (2-hydroxypropanoate) was 1.78 g (4.38 mmol, 57%). Elemental analysis C ₁₈ H _{30 O 10} (%): C, 53.19; H, 7.44; O,

39.37. Found: C, 53.3; H, 7.6. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.03 (q, Z _H -n = 7.1 Hz, 2H, OCZZ (Me) COO), 4.24 (q, -ι-κ) = 6.9 Hz, 2H, HOCZZ (Me)), 3.95-3.90 (m, 4H, COOCZZ ₂ ^Hex ),

1.47 (d, J _H-H = 7.1 Hz, 6H, CH (CZZ ₃ ) COO), 1.24-1.20 (m, 12 H, HOCZZ (Me) and ZO ^ex ), 1 , 03-0.99 (m, 2H, 2H ^Hx ). ¹³ C NMR (125 MHz, C6D6, 298K): δ 175.4 (COOHex), 170.4 (C (Me) COO), 72.0 (OC (Me) COOHex), 67.0 (HOC (Me) , 65.5 (OCH 2 (CH 2) 4 CH 2 O), 28.7 and 25.5 (C ^Hex ), 20.7 (OC (CH 3) COO), 16.7 (HOC (CH ₃ ) COO).

Example 92. Preparation of hexane-1,6-diylbis (oxy (25,2'S) -1-oxopropane-1,2-diyl) (2S, 2'5) -bis (2-hydroxypropanoate) from L-lactide and hexane -1,6-diol initiated by HBr

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diylbis (oxy (25 ', 2'S) -1-oxopropane-1,2-diyl) (25', 2Y) -bis (2-hydroxypropanoate) was 1.80 g (4). , 43 mmol, 58%). Elemental analysis for C ₁₈ H ₃₀ O ₁₀ (%): C, 53.19; H, 7.44; O,

39.37. Found: C, 53.4; H, 7.6. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.03 (q, J _H -h = 7.1 Hz, 2H, OCZ 2 (Me) COO), 4.24 (q,, _{[ 1H} = 6.9 Hz, 2H, HOCZ / (Me)), 3.95-3.90 (m, 4H, COOCZZ ₂ ^Hex)

1.47 (d, J H-H = 7.1 Hz, 6H, CH (CZZ ₃ ) COO), 1.24-1.20 (m, 12H, HOCZZ (Me) and Z / ¹¹ '), 1 , 03-0.99 (m, 2H, ZU '). ¹³ C NMR (125 MHz, C6D6, 298K): δ 175.4 (COOHex), 170.4 (C (Me) COO), 72.0 (OC (Me) COOHex), 67.0 (HOC (Me)) ), 65.5 (OCH 2 (CH 2) 4 CH 2 O), 28.7 and 25.5 (C ^Hex ), 20.7 (OC (CH 3) COO), 16.7 (HOC (CH ₃ ) COO).

Example 93. Preparation of hexane-1,6-diylbis (oxy (2S, 2'5) -1-oxopropane-1,2-diyl) (25,2'S) -bis (2-hydroxypropanoate) from L- lactide and hexane-1,6-diol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of Z-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of H1 (conc. 67%, 0.51 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. Subsequently, all were evaporated under reduced pressure

The volatiles were removed and the residue obtained was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diylbis (oxy (25,2'5) -1-oxopropane-1,2-diyl) (25,2'S) -bis (2-hydroxypropanoate) was 1.72 g (4.23 mmol). , 55%). Elemental analysis for C ₁₈ H _{30 O 10} (%): C, 53.19; H, 7.44; O,

39.37. Found: C, 53.0; H, 7.3. H NMR (500 MHz, C ₆ D _6, 298K) δ 5.03 (q, 7 _H -H = 7.1 Hz, 2H, OC // (Me) COO), 4.24 (q, J _H-H = 6.9 Hz, 2H, HOC // (Me)), 3.95-3.90 (m, 4H, COOCH ₂ ^Hex)

1.47 (d, J _H -H = 7.1 Hz, 6H, CH (C / 7 ₃₎ COO), 1.24 to 1.20 (m, 12 H, HOC / 7 (Me) and Z / ¹¹ "), 1.03-0.99 (m, 2H, D ^Hex ). ¹³ CNMR (125 MHz, C6D6, 298K): δ 175.4 (COOHex), 170.4 (C (Me) COO), 72.0 (OC (Me) COOHex), 67.0 (HOC (Me)) , 65.5 (OCH 2 (CH 2) 4 CH 2 O), 28.7 and 25.5 (C ^Hex ), 20.7 (OC (CH 3) COO), 16.7 (HOC (CH ₃ ) COO).

Example 94. Preparation of hexane-1 ', 6-diylbis (oxy (2 H, 2 H) -1-oxopropane-1,2-diyl) (2 H, 2,7 Z) -bis (2-hydroxypropanoate) from D-lactide and HCl-initiated hexane-1,6-diol

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diylbis (oxy (2 R, 2 R) -1-oxopropane-1,2-diyl) (2 H, 2 H) -bis (2-hydroxypropanoate) was 1.75 g (4.31 mmol, 56%). Elemental analysis for C ₁₈ H ₃₀ O ₁₀ (%): C, 53.19; H, 7.44; O,

39.37. Found: C, 53.0; H, 7.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.0 Hz, 2H, OC // (Me) COO), 4.25 (q, J _H-N = 7.0 Hz, 2H, HOC7 / (Me)), 3.98-3.92 (m, 4H, COOCD ₂ ^Hex)

1.50 (d, J _H-H = 7.1 Hz, 6H, CH (C // ₃ ) COO), 1.26-1.21 (m, 12 H, HOC // (Me) and // .Delta., 1.05-1.00 (m, 2H, 1H). ¹³ CNMR (125 MHz, C6D6, 298K): δ 176.0 (COOHex), 170.4 (C (Me) COO), 72.2 (OC (Me) COOHex), 66.8 (HOC (Me)) , 65.6 (OCH 2 (CH 2) 4 CH 2 O), 28.9 and 25.5 (C ^Hex ), 20.3 (OC (CH 3) COO), 16.2 (HOC (CH ₃ ) COO).

Example 95. Preparation of hexane-1,6-diylbis (oxy (2 R, 2 R) -1-oxopropane-1,2-diyl) (2 H, 2 H) -bis (2-hydroxypropanoate) from D-lactide and HBr-initiated hexane-1,6-diol

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diylbis (oxy (2 / Z, 2Z) -1-oxopropane-1,2-diyl) (2 H, 2 H) -bis (2-hydroxypropanoate) was 1.74 g (4 , 28 mmol, 56%). Elemental analysis C ₈ H _{30 0} Oi (%): C, 53.19; H, 7.44; O,

39.37. Found: C, 53.3; H, 7.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.0 Hz, 2H, OCD [Me) COO), 4.25 (q, J _H- H = 7.0 Hz, 2H, HOCtf (Me)), 3.98-3.92 (m, 4 H, COOC / 7 ₂ ^Hex)

1.50 (d, J _H-H = 7.1 Hz, 6H, CH (C // ₃ ) COO), 1.26-1.21 (m, 12 H, HOC // (Me) and // ""), 1.05-1.00 (m, 2H, // ""). ³ C NMR (125 MHz, C6D6, 298K): δ 176.0 (COOHex), 170.4 (C (Me) COO), 72.2 (OC (Me) COOHex), 66.8 (HOC (Me) ), 65.6 (OCH 2 (CH 2) 4 CH 2 O), 28.9 and 25.5 (C ^Hex ), 20.3 (OC (CH 3) COO), 16.2 (HOC (CH ₃ ) COO).

-39GB 306988 Β6

Example 96. Preparation of hexane-1,6-diylbis (oxy (2R, 2'R) -1-oxopropane-1,2-diyl) (2R, 2'R) -bis (2-hydroxypropanoate) from D-lactide and hexane- Of 1,6-diol initiated by HI

A 25 mL round bottom flask was charged with 1.1 g of D-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diylbis (oxy (2 R, 2 R) -1-oxopropane-1,2-diyl) (2 R, 2 R) -bis (2-hydroxypropanoate) was 1.80 g ( 4.43 mmol, 58%). Elemental analysis for C ₁₈ H ₃₀ O 10 (%): C, 53.19; H, 7.44; O,

39.37. Found: C, 53.4; H, 7.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, 7.0 Hz,

2H, OCD (Me) COO), 4.25 (q, 7 _H -H = 7.0 Hz, 2H, HOCW (Me)), 3.98-3.92 (m, 4H, COOCD ₂ ^Hex)

1.50 (d. _H = 7.1 Hz, 6H, CH (C77 ₃₎ COO), 1.26 to 1.21 (m, 12 H, HOCD (Me) and D ^Hex) 1.05 1.00 (m, 2H, 76% ^lex ). ¹³ CNMR (125 MHz, C6D6, 298K): δ 176.0 (COOHex), 170.4 (C (Me) COO), 72.2 (OC (Me) COOHex), 66.8 (HOC (Me)) , 65.6 (OCH 2 (CH 2) 4 CH 2 O), 28.9 and 25.5 (C ^Hex ), 20.3 (OC (CH 3) COO), 16.2 (HOC (CH ₃ ) COO).

Example 97. Preparation of hexane-1,6-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and hexane-1,6-diol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.78 g (4.38 mmol, 57%). Elemental analysis for C ₁₈ H ₃₀ O 10 (%): C, 53.19; H, 7.44; O, 39.37. Found: C, 53.3; H, 7.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.01 (q, J _H -h = 7.0 Hz, 2H, OCD (Me) COO),

4.20 (q, Λ _H = 6.8 Hz, 2H, HOCD (Me)), 3.97-3.93 (m, 4 H, COOC / ₂ 7 ^Hex), 1.46 (d, ./ " H = 6.8 Hz, 6H, CH (CD 3) COO), 1.26-1.22 (in, 12 H, HOCD (Me) and 7Z ^ex ), 1.03-0.97 (m, 2H, // ^lex ). ¹³ C NMR (125 MHz, C 6 D _6, 298K): δ 174.8 (COOHex), 170.1 (C (Me) COO), 72.0 (OC (Me) COOHex), 65.9 (HOC (Me) ), 65.2 (OCH ₂ (CH ₂ ) ₄ CH ₂ O), 29.0 and 25.3 (C ^Hex ), 20.1 (OC (CH ₃ ) COO), 16.0 (HOC (CH ₃₎ ) COO).

Example 98. Preparation of hexane-1,6-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and hexane-1,6-diol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.81 g (4.45 mmol, 58%). Elemental analysis C ₁₈ H _{30 O 10} (%): C, 53.19; H, 7.44; O, 39.37. Found: C, 53.0; H, 7.2. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.01 (q, J _H -h = 7.0 Hz, 2H, OCD (Me) COO),

4.20 (q, J _H-H = 6.8 Hz, 2H, HOC 77 (Me)), 3.97-3.93 (m, 4H, COOCD ₂ ^Hex ), 1.46 (d, J, _w = 6.8 Hz, 6H, CH (C / 7 ₃₎ COO), 1.26 to 1.22 (m, 12 H, HOCD (Me) and // * "), 1,03-0, 97 (m, 2H, 7 / ^lex ). ¹³ CNMR

-40EN 306988 B6 (125 MHz, C ₆ D ₆ , 298K): δ 174.8 (COOHex), 170.1 (C (Me) COO), 72.0 (OC (Me) COOHex), 65.9 ( HOC (Me)), 65.2 (OCH ₂ (CH ₂ ) ₄ CH ₂ O), 29.0 and 25.3 (C ^Hex ), 20.1 (OC (CH ₃ ) COO), 16.0 ( HOC (CH ₃ ) COO).

Example 99. Preparation of hexane-1,6-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and hexane-1,6-diol initiated by HI

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Subsequently, 3.0 g of hexane-1,6-diol (0.025 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) were added, and the resulting reaction mixture was stirred for an additional 15 min. All volatiles were then evaporated under reduced pressure and the residue was washed with dichloromethane. The product was extracted with benzene and dried to constant weight at 40 ° C / 1 mbar.

The yield of hexane-1,6-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.77 g (4.36 mmol, 57%). Elemental analysis for C ₁₈ H ₃₀ O ₁₀ (%): C, 53.19; H, 7.44; O, 39.37. Found: C, 53.3; H, 7.5. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.01 (q, J _H -h = 7.0 Hz, 2H, OCH (Me) COO),

4.20 (q, J = 6.8 Hz, 2H, HOC / 7 [Me)), 3.97-3.93 (m, 4 H, COOC / ₂ 7 ^Hex), 1.46 (d, / _H! i = 6.8 Hz,

6H, CH (C7 / ₃ ) COO), 1.26-1.22 (m, 12H, HOCH (Me) and 1.03-0.97 (m, 2H, rf ™)) ¹³ C NMR (125 MHz, C6D6, 298K): δ 174.8 (COOHex), 170.1 (C (Me) COO), 72.0 (OC (Me) COOHex), 65.9 (HOC (Me)), 65.2 (OCH 2 (CH 2) 4 CH 2 O), 29.0 and 25.3 (C ^Hex ), 20.1 (OC (CH 3) COO), 16.0 (HOC (CH ₃ ) COO).

Example 100. Preparation of decan-1, 10-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and decane-1,10-diol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 35 ° C where it was stirred vigorously for 15 min. Subsequently, 6.0 g of decan-1, 10-diol (0.034 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 25 min. All volatiles were then evaporated under reduced pressure. The product was extracted with benzene.

The yield of decane-1, 10-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.94 g (4.19 mmol, 55%). Elemental analysis for C ₂₂ H _{38 O 10} (%): C, 57.13; H, 8.28; O, 34.59. Found: C, 57.3; H, 8.4. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H -h = 7.0 Hz, 2H, OC // (Me) COO),

4.25 (q, 7 _H -H = 7.0 Hz, 2H, HOC77 (Me)), 3.97-3.94 (m, 4 H, COOC / 7 ₂ ^Dek), 1.48 (d, JH -h = 7.0 Hz, 6H, CH (C773) COO), 1.39 to 1.37 (m, 4H, / 7), 1.24-1.22 (m, 10H, H ^lck and HOCtf ( Me)), 1.12 (br s, 8H, H ^{kk). 13} C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 175.7 (COODek), 170.8 (C (Me) COO), 69.0 (OC (Me) COODek), 66.8 (HOC (Me) ), 67.3 (CH ₂ (CH ₂ ) ₉ O), 65.9 ((CH ₂ ) ₉ CH ₂ O), 30.0, 29.7, 29.1 and 26.3 (C ^Dec ) , 21.0 (OC (CH ₃ ) COO), 17.4 (HOC (CH ₃ ) COO).

Example 101. Preparation of decr-1, 10-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) from rac-lactide and decr-1, 10-diol initiated by HBr

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 30 ° C where it was stirred vigorously for 20 min. Then 6.0 g of decane-1, 10-diol (0.034 mol) + 0.05 ml of HBr (conc. 48%, 0.44 mmol) were added, and the resulting reaction mixture was stirred for an additional 25 min. All volatiles were then evaporated under reduced pressure. The product was extracted with benzene.

The yield of decan-1, 10-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.99 g (4.30 mmol, 56%). Elemental analysis for C ₂₂ H ₃₈ O ₁₀ (%): C, 57.13; H, 8.28; O, 34.59. Determined:

. Al _

C, 57.0; H, 8.2. NMR (500 MHz, C ₆ D _O, 298K) δ 5.05 (q, J _H-H = 7.0 Hz, 2H, OCZ / (Me) COO)

4.25 (q, J _H-H = 7.0 Hz, 2H, HOCZZ (Me)), 3.97-3.94 (m, 4H, ₂ COOCZZ ^Dek), 1.48 (d, J H-H = 7.0 Hz, 6H, CH (CZZ3) COO), 1.39-1.37 (m, ZZ ° ^ek ), 1.24-1.22 (m, 10H, ZZ ° ^ek and HOCZZ (Me) ), 1.12 (br s, 8H, ZZ ° ^{s). I3} C NMR (125 MHz, C 6 D _6, 298K): δ 175.7 (COODek), 170.8 (C (Me) COO), 69.0 (OC (Me) COODek), 66.8 (HOC (Me ), 67.3 (CH ₂ (CH ₂ ) ₉ O), 65.9 ((CH ₂ ) ₉ CH ₂ O), 30.0, 29.7, 29.1 and 26.3 (C ^Dec ) , 21.0 (OC (CH ₃ ) COO), 17.4 (HOC (CH ₃ ) COO).

Example 102. Preparation of decane-1, 10-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanol) from rac-lactide and decane-1, 10-diol initiated by HI

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 70 ° C where it was stirred vigorously for 15 min. Then 6.0 g of decan-1, 10-diol (0.034 mol) + 0.05 ml of HI (conc. 67%, 0.51 mmol) were added, and the resulting reaction mixture was stirred for an additional 25 min. All volatiles were then evaporated under reduced pressure. The product was extracted with benzene.

The yield of decan-1, 10-diylbis (oxy-1-oxopropane-1,2-diyl) bis (2-hydroxypropanoate) was 1.96 g (4.24 mmol, 56%). Elemental analysis for C ₂₂ H ₃₈ O ₁₀ (%): C, 57.13; H, 8.28; O, 34.59. Found: C, 57.3; H, 8.1. 1 H NMR (500 MHz, C ₆ D ₆ , 298K): δ 5.05 (q, J _H + = 7.0 Hz, 2H, OC77 (Me) COO),

4.25 (q, J _H-H = 7.0 Hz, 2H, HOC77 (Me)), 3.97-3.94 (m, 4H, ₂ COOC77 ^Dek), 1.48 (d, J H-H = 7.0 Hz, 6H, CH (C773) COO), 1.39 to 1.37 (m, 4H, / ° ^s), 1.24-1.22 (m, 10H, ZZ ° ^ek and HOCZZ (Me)), 1.12 (br s, 8H, H ^{, ck} ). ¹³ C NMR (125 MHz, C ₆ D ₆ , 298 K): δ 175.7 (COODek), 170.8 (C (Me) COO), 69.0 (OC (Me) COODek), 66.8 (HOC (Me) ), 67.3 (CH ₂ (CH ₂ ) ₉ O), 65.9 ((CH ₂ ) ₉ CH ₂ O), 30.0, 29.7, 29.1 and 26.3 (C ^Dec ) , 21.0 (OC (CH ₃ ) COO), 17.4 (HOC (CH ₃ ) COO).

Example 103. Preparation of 1 - [(3-ethyloxetan-3-yl) methoxy] -1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and trimethylolpropane oxetane initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 50 ° C where it was stirred vigorously for 60 min. Then 3.0 mL of trimethylolpropane oxetane (TMPO, 0.026 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 40 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1 - [(3-ethyloxetan-3-yl) methoxy] -1-oxopropan-2-yl 2-hydroxypropanoate was 0.85 g (3.26 mmol, 43%). Elemental Analysis Calcd ₂ H ₂₀ O 6 (%): C, 55.37; H, 7.74; O, 36.88. Found: C, 55.5; H, 7.8. 'H NMR (500 MHz, CDC1 _3, 298K) δ 5.05 (q, 7 _H -H = 7.0 Hz, 1H, OCZZ (Me) COO), 4.30-4.25 (m, 3H HOCZZ (Me) and COOCZC), 4.05-3.94 (m, 4H, CZ ₂ ^0x ), 1.62 (m, 7H-h = 7.2 Hz, 2H, CZZ 2 CH 3), 1.46 ( d, h = 7.0 Hz, 3 H, CH (CZ 2 O 3) COO), 1.21 (d, Z 2 = 7.0 Hz, 3 H, HOC 2 Z (Me)), 1.04 (t, J H- h = 7.0 Hz, 3H, OCH 2 CNZ 3). ¹³ C NMR (125 MHz, CDCl 3, 298K): δ 176.1 (COOOx), 171.2 (C (Me) COO), 78.2 (CH ₂ ^Ox ), 69.4 (OC (Me) COOOx) , 67.4 (HOC (Me)), 65.9 (COOCH 2), 42.9 (C ° ^x ), 26.8 (CZ ₂ CH ₃ ), 21.1 (OC (CH ₃ ) COO), 17.7 (HOC (CH ₃ ) COO), 11.3 (CH ₂ CH ₃ ).

Example 104. Preparation of 1- (hexadecanyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate from raclactide and hexadecan-1-ol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 60 ° C where it was stirred vigorously for 20 min. Subsequently, 2.5 g of hexadecan-1-ol (10.31 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) were added,

The reaction mixture was stirred for an additional 30 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dichloromethane and then dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- (hexadecanyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate was 1.15 g (2.97 mmol, 39%). Elemental analysis C ₂₂ H 4 ₂ O ₅ (%): C, 68.35; H, 10.95; O, 20.69. Found: C, 68.1; H, 10.8. ¹ H NMR (500 MHz, CDCl 3, 298K): δ 5.03 (q, JH-h = 7.0 Hz, 1H, OCfl (Me) COO), 4.38 (q, JH-h = 6.8 Hz, 1H, HOCfl (Me)), 3.20 (t, JH-H = 7.2 Hz, 2H, COOC772 ^hexD), 1.62 (br s, 2H, fl ^{31 "0),} 1,58- 1.41 (m, 9H, OCH (Cf13) COO a / Z ^HexD ), 1.36-1.33 (m, 4H, ^{J exD} ), 1.25-1.17 (m, 19H, HOCH (Cfl3)) ) and FL ^{11 '13),} 1.02 (t, JH-H = 7.0 Hz, 3H, ₃ ^hexD Cfl). ¹³ C NMR (125 MHz, CDCl 3, 298K): δ 175.8 (COOC ^HexD ), 171.0 (C (Me) COO), 69.4 (OC (Me) COOHexD), 67.0 (HOC (Me) ), 60.2 (COOC ^HexD ), 38.1, 37.6, 31.3, 31.0, 25.2 and 23.7 (C ^HexD ), 21.0 (OC (CH 3) COO), 17.5 (HOC (CH ₃ ) COO), 15.1 and 14.6 (C ^HexD ).

Example 105. Preparation of 1- (octadecanyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and octadecan-1-ol initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 60 ° C where it was stirred vigorously for 20 min. Then 2.70 g of octadecan-1-ol (10.00 mol) + 0.05 ml of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 30 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dichloromethane and then dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- (octadecanyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate was 1.17 g (2.82 mmol, 37%). Elemental analysis for C ₂₄ H ₄₆ O ₅ (%): C, 69.52; H, 11.18; O, 19.29. Found: C, 69.8; H, 11.4. 1 H NMR (500 MHz, CDCl ₃ , 298K): δ 5.01 (q, J _HH = 7.5 Hz, 1H, OCl [Me] COO), 4.39 (q, J _H -h = 7, 2 Hz, 1H, HOCfl (Me)), 3.33 (t, J _H-H = 7.0 Hz, 2H, ₂ COOCfl ^OktD), 1.64 to 1.60 (m, 2H, FL ° ^KTD) , 1.59-1.44 (m, 9H, OCH (Cf13) COO and ^{flt kD} ), ^1.38-1.34 (m, 4H, ^{flt ktD} ), 1.27-1.15 (m , 23H, HOCH (Cfl3) and fl ° ^KTD) '0.98 (t, JH-H = 6.8 Hz, 3H, CH3 ^{0k, D). 13} C NMR (125 MHz, CDCl 3, 298K): δ 173.6 (COOC ° ^{k, D} ), 170.8 (C (Me) COO), 69.6 (OC (Me) COOOktD), 66.4 ( HOC (Me)), 61.7 (COOC ^Oct ), 38.3, 37.4, 31.8, 31.2, 25.2, 25.0 and 23.7 (C ° ^ktD ), 21.2 (OC (CH ₃ ) COO), 17.4 (HOC (CH ₃ ) COO), 15.0 and 14.4 (C ^OktD ).

Example 106. Preparation of 1- (cis-9-octadecenyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and cis-9-octadecen-1-ol initiated with HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 40 ° C where it was stirred vigorously for 15 min. Subsequently, 3.20 mL of cis-9-octadecen-1-ol (10.12 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 20 min. All volatiles were then evaporated under reduced pressure. The residue was washed with hexane and dichloromethane and then dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- (cis-9-octadecenyloxy) -1-oxopropan-2-yl 2-hydroxypropanoate was 1.32 g (3.20 mmol, 42%). Elemental analysis for C 4 H 44 O 5 (%): C, 69.86; H, 10.75; O, 19.39. Found: C, 69.7; H, 10.7. 1 H NMR (500 MHz, CDCl ₃ , 298K): δ 5.16-5.05 (m, 3H, OC // (Me) COO and CH = ^CHOktD ), 4.39 (q, JH-h = 7) 1 Hz, 1H, HOCf1 (Me)), 3.18 (t, JH-h = 7.1 Hz, 2H, COOCf12 ^oct ), 1.66-1.63 (m, 2H, fl ° ^ktD ), 1.58-1.42 (m, 9H, OCH (Cf13) COO and ^{flt kD} ), 1.37-1.32 (m, 4H, ^{flt ktD} ), 1.20 (br s, 19H, HOCH) (Cfl3) and FL ^0130), 0.99 (t, JH-H = 7.0 Hz, 3H, ₃ ^0ktD Cfl). ^I3 C NMR (125 MHz, CDC1 _3, 298K): δ 175.3 (COOC ° ^KTD), 172.4 (C (Me) COO), 131.5

(CH = CH ^octD ), 69.3 (OC (Me) COOOktD), 64.7 (HOC (Me)), 60.3 (COOC ° ^{k, D} ), 38.0, 36, 1, 33.4,

33.2, 31.5, 25.0, 24.3, and 23.1 (C ° ^ktD ), 21.0 (OC (CH ₃ ) COO), 16.2 (HOC (CH ₃ ) COO), 15.1 (C ° ^ktD ).

Example 107. Preparation of 1- {2,2-bis [(prop-2-en-1-yloxy) methyl] butoxy} -1-oxopropan-2-yl 2-hydroxypropanoate from rac-lactide and trimethylolpropane diallyl ether initiated by HCl

To a 25 mL round bottom flask was charged 1.1 g of rac-lactide (7.63 mmol) and 3 mL of toluene. The resulting solution was heated to 40 ° C where it was stirred vigorously for 60 min. Then 5.0 mL of trimethylolpropane diallyl ether (TMPDE, 0.022 mol) + 0.05 mL of HCl (conc. 36%, 0.58 mmol) was added, and the resulting reaction mixture was stirred for an additional 60 min. All volatiles were then evaporated under reduced pressure. The residue was washed with dichloromethane and dried to constant weight at 40 ° C / 1 mbar.

The yield of 1- {2,2-bis [(prop-2-en-1-yloxy) methyl] butoxy} -1-oxopropan-2-yl 2-hydroxypropanoate was 1.04 g (2.90 mmol, 38%) . Elemental analysis for C ₁₈ H ₃₀ O ₇ (%): C, 60.32; EI, 8.44; O, 31.25. Found: C, 60.2; H, 8.3. Ή NMR (500 MHz, CDCl ₃ , 298K): δ 5.82-5.76 (m, 2H, CH ₂ CH ^tmpde ), 5.24 (d, 1H-h = 10.0 Hz, 2H, CH ₂ Cl ₂ ) ( ^TMPDE ), 5.13 (d, ZH-h = 10.4 Hz, 2H, CH ₂ CH ^TMPDE ), 5.08 (q, 7H-h = 7.0 Hz, 1H, OCtf (Me) COO) 4.37 (q, 1H H = 7.0 Hz, 1H, HOCH (Me)), 3.93 (d, J H-H = 5.5 Hz, 4H, CHCl ³ F ² O ^TMPDE ), 3.62 (br s 2H, COOC / Y), 3.34 (d, J H-H = 9.1 Hz, 2H, C / Z ₂ C ™ ^pde ), 3.27 (d, J H-H = 9.0 Hz, 2H C / Z2C ™ ^PDE ), 1.43 (d, J H-H = 6.5 Hz, 3H, CH (C H ₃ ) COO), 1.32 (q, 7 _H-H = 6.5 Hz, 2H , C77 _{2 CH3} ^TMPD), 1.20 (d, ZH-H = 6.8 Hz, 3H, HOCtf (Me)), 0.83 (t, ZH-H = 7.6 Hz, 3H, CH2CZ73 ™ ^PDE ). ¹³ C NMR (125 MHz, CDCl 3, 298K): δ 175.2 (COOTMPDE), 172.8 (C (Me) COO), 134.2, 116.7, 73.3 and 72.6 (C ^TMPDE ) , 69.1 (OC (Me) COOTMPDE), 68.1 (HOC (Me)), 62.3 ( ^{COOCH2 TMDPE} ), 41.7 and 21.8 (C ^TMDPE ), 20.2 (OC (CH3)) COO), 17.4 (HOC (CH ₃ ) COO), 8.8 (C ^TMDPE ).

Industrial applicability

Lactyl lactate esters can be used in the food, cosmetic and pharmaceutical industries and applied chemistry as carriers of active ingredients, e.g., drugs, fillers.

Claims (6)

PATENT CLAIMS A process for the preparation of a lactyl lactate hydrocarbyl ester from a lactide, which comprises contacting the lactide with a hydrocarbyl alcohol and a hydrogen halide to form a lactyl lactate hydrocarbyl ester, wherein the hydrocarbyl alcohol is selected from polyethylene glycols up to 20,000 g / mol and aliphatic or alicyclic, aromatic alcohols having 1 to 30 carbon atoms and optionally at least one double and / or triple bond, and 1 to 5 hydroxyl groups, wherein optionally one or more -CH ₂ - groups may be replaced by -O-. 2. The process of claim 1 wherein the hydrocarbyl alcohol is selected from the group consisting of polyethylene glycols, glycols, glycerol, monohydroxy alcohols. 3. The process of claim 1 wherein the hydrocarbyl alcohol is selected from the group consisting of methanol, propan-1-ol, butan-1-ol, propan-2-ol, 2-methyl propan-2-ol, 2-ethylhexane- 1-ol, phenol, cyclohexanol, trimethylolpropane oxetane, trimethylolpropane diallyl ether, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol, octadecan-1 -ol, cis-9-octadecen-1-ol, hexadecan-1-ol. -44EN 306988 B6 Process according to any one of the preceding claims, characterized in that the reaction is carried out in an aromatic solvent. A process according to any one of the preceding claims, characterized in that the reaction is carried out at a temperature in the range of 35 to 90 ° C for 15 to 90 minutes. Process according to any one of the preceding claims, characterized in that the reaction mixture comprises lactide, hydrocarbyl alcohol in a molar excess over the lactide, and 0.04 to 0.1, preferably 0.06 to 0.08 molar equivalents of hydrogen halide solution based on to lactide.