13076-17-0

Basic information

• Product Name: D(+)-LACTIDE
• Synonyms: PURASORB(R) D;D(+)-LACTIDE;(3R-CIS)-3,6-DIMETHYL-1,4-DIOXANE-2,5-DIONE;(2R,5R)-2,5-Dimethyl-1,4-dioxane-3,6-dione;(3R)-3β,6β-Dimethyl-1,4-dioxane-2,5-dione;(3R,6R)-3,6-Dimethyl-1,4-dioxane-2,5-dione;3β,6β-Dimethyl-1,4-dioxin-2,5(3H,6H)-dione;1,4-Dioxane-2,5-dione,3,6-diMethyl-, (3R,6R)-
• CAS NO: 13076-17-0
• Molecular Formula: C₆H₈O₄
• Molecular Weight: 144.13
• Mol File: 13076-17-0.mol
• Article Data: 10

Chemical Properties

• Melting Point: 96.5-97.5 °C
• Boiling Point: 285.469 °C at 760 mmHg
• Flash Point: 150.578 °C
• Appearance: /
• Density: 1.186 g/cm³
• Vapor Pressure: 0.003mmHg at 25°C
• Refractive Index: 1.429
• Storage Temp.: Sealed in dry,Room Temperature
• Solubility: Chloroform (Slightly), Toluene (Slightly)
• CAS DataBase Reference: D(+)-LACTIDE(CAS DataBase Reference)
• NIST Chemistry Reference: D(+)-LACTIDE(13076-17-0)
• EPA Substance Registry System: D(+)-LACTIDE(13076-17-0)

Safety Data

• Hazardous Substances Data: 13076-17-0(Hazardous Substances Data)

Usage

Chemical Properties

white to almost white powder to crystal.

Uses

D-(+)-Lactide is the cyclic di-ester of lactic acid (L113490), an by product that is produced by muscle cells and red blood cells when the body breaks down carbohydrates for energy during times of low oxygen levels. Lactide can be polymerized to polylactic acid using a suitable catalyst go give materials of useful properties.

InChI:InChI=1/C6H8O4/c1-3-5(7)10-4(2)6(8)9-3/h3-4H,1-2H3/t3-,4-/m1/s1

Synthetic route

stannous lactate → D-lactide (13076-17-0)

Conditions	Yield
With 1-acetylthiosemicarbazide at 110 - 180℃; under 1 Torr; for 2h; Temperature; Reagent/catalyst; Pressure;	95.82%

D-Alanine (338-69-2) → D-Lactic acid (10326-41-7) + D-lactide (13076-17-0)

Conditions	Yield
With sulfuric acid; sodium nitrite In water at 0 - 20℃; stereoselective reaction;	A 58% B < 3 %Spectr.

D-Lactic acid (10326-41-7) → D-lactide (13076-17-0)

Conditions	Yield
Stage #1: D-Lactic acid at 160℃; under 50 Torr; for 4h; Inert atmosphere; Industrial scale; Stage #2: With biogenic guanidine creatinine (CR) at 200℃; under 8 Torr; for 2h; Industrial scale;	46.8%

Reaxys ID: 11369848 → hexalactide + trilactide (859046-55-2) + C12H16O8 + C15H20O10 (859046-57-4) + C21H28O14 + (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) + L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
at 60 - 400℃; for 0.566667h; Product distribution / selectivity; Pyrolysis;	A 4.51% B 3.26% C 5.59% D 6.02% E 1.88% F 18.28% G n/a H n/a

...Expand

Reaxys ID: 11369849 → hexalactide + trilactide (859046-55-2) + C12H16O8 + C15H20O10 (859046-57-4) + (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) + L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
at 60 - 400℃; for 0.566667h; Product distribution / selectivity; Pyrolysis;	A 0.46% B 0.5% C 1.65% D 0.75% E 12.17% F n/a G n/a

Reaxys ID: 11369849 → (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) + L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
at 60 - 400℃; for 0.433333 - 0.566667h; Product distribution / selectivity; Pyrolysis;	A 6.08% B n/a C n/a

Reaxys ID: 11369849 → C12H16O8 + C15H20O10 (859046-57-4) + L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
at 60 - 300℃; for 0.4h; Product distribution / selectivity; Pyrolysis;	A 0.28% B 0.2% C n/a D n/a

poly(L-lactic acid) → LACTIC ACID (849585-22-4) + (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) + L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
tin(II) octanoate at 210 - 230℃; under 22.5023 Torr; for 1 - 2h; Product distribution / selectivity;
zinc stearate at 210 - 230℃; under 22.5023 Torr; for 1 - 2h; Product distribution / selectivity;
tin(II) octanoate at 210 - 230℃; under 22.5023 Torr; for 1 - 2h; Product distribution / selectivity;

Reaxys ID: 11363805 → L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
tin octanoate at 60 - 300℃; for 0.4h; Product distribution / selectivity; Pyrolysis;

Reaxys ID: 11369849 → L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
at 60 - 320℃; for 0.433333h; Product distribution / selectivity; Pyrolysis;

(3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) → L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
Na-ethylhexanoate at 160℃; for 15h; Product distribution / selectivity; Racemisation; Parr reactor;
Multi-step reaction with 2 steps 1: potassium phosphate / ethyl acetate / 168 h / 20 °C 2: 1,8-diazabicyclo[5.4.0]undec-7-ene / toluene / 4 h / 110 °C View Scheme

L-Lactic acid (79-33-4) → (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) + L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
Stage #1: L-Lactic acid In water at 170℃; under 80 Torr; for 3h; Stage #2: tin catalyst at 220℃; under 10 - 15 Torr; Product distribution / selectivity;
With potassium hydroxide; stannous octoate at 150 - 240℃; under 7.50075 Torr; Product distribution / selectivity;

(3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) → D-lactide (13076-17-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium phosphate / ethyl acetate / 168 h / 20 °C 2: 1,8-diazabicyclo[5.4.0]undec-7-ene / toluene / 4 h / 110 °C 3: 1,8-diazabicyclo[5.4.0]undec-7-ene / toluene / 48 h / 20 °C View Scheme

3,6-dimethyl-1,4-dioxane-2,5-dione → (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) + L,L-dilactide (4511-42-6) + D-lactide (13076-17-0)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 110℃; for 4h; optical yield given as %ee;

L,L-dilactide (4511-42-6) → (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) + D-lactide (13076-17-0)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 20℃; for 48h;
With sodium hydride In mineral oil at 200℃; for 6h; Reagent/catalyst; Temperature; stereoselective reaction;

(3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione (13076-19-2) + L,L-dilactide (4511-42-6) → D-lactide (13076-17-0)

Conditions	Yield
With sodium nitrite at 180℃; for 2h; Reagent/catalyst; Temperature; stereoselective reaction;

hexahydro-2H-oxepin-2-one (502-44-3) + glycolide (502-97-6) + D-lactide (13076-17-0) → polymer, Mn: 48.0 kDa, Mw/Mn: 1.3; monomer(s): L-lactide; ε-caprolactone; glycolide

Conditions	Yield
With zirconium acetylacetonate at 100℃;	92%

diethylamine (109-89-7) + D-lactide (13076-17-0) → (R)-N,N-diethyl-2-hydroxypropanamide

Conditions	Yield
Stage #1: diethylamine With aluminum (III) chloride In dichloromethane at 35℃; for 0.5h; Stage #2: D-lactide In dichloromethane at 35℃; for 1h;	82%

propan-1-ol (71-23-8) + D-lactide (13076-17-0) → (2R)-2-hydroxypropanoic acid, 2-propyloxy-(1R)-1-methyl-2-oxoethylester

Conditions	Yield
With Pseudomonas fluorescens GK13 medium-chain-length-PHA depolymerase In toluene at 80℃; for 24h; Inert atmosphere; Enzymatic reaction;	80%

ethanol (64-17-5) + D-lactide (13076-17-0) → (R)-Ethyl lactate (7699-00-5)

Conditions	Yield
With hydrogenchloride In toluene	76%

D-lactide (13076-17-0) → polylactide, Mn(GPC) = 13500, Mw/Mn(GPC) = 1.08, isotactic, monomer(s): D-lactide

Conditions	Yield
With tris(methylene)amine[tris(4,6-di-tBu-phenolate)]-(OiPrZr) In chloroform-d1 at 20℃; Kinetics;	75%

D-lactide (13076-17-0) + poly-ε-caprolactone → poly(D-lactide-b-ε-caprolactone) diblock copolymer; monomers: D-lactide; poly(ε-caprolactone)

D-lactide (13076-17-0) → poly-(D-lactide), isotactic, spectroscopic Mn=6400, chromatographic Mn=5900, Mw/Mn=1.08; monomer(s): D-lactide

Conditions	Yield
With (R,R)-cyclohexylsalen aluminum isopropoxide In toluene at 70℃; Kinetics;

D-lactide (13076-17-0) → L-lactide polymer

Conditions	Yield
With [C(Htbpoa)2Mg] In toluene at 20℃; for 0.25h;	100 % Turnov.

D-lactide (13076-17-0) → poly(D-lactide), MW 1.45E4 g/mol; monomer(s): D-lactide

Conditions	Yield
In toluene

poly(ethylene glycol) 4600 + D-lactide (13076-17-0) → polymer(D-lactide)-block-poly(ethylene glycol), Mn 6400 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

poly(ethylene glycol) 4600 + D-lactide (13076-17-0) → poly(D-lactide)-block-poly(ethylene glycol), Mn 7700 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

poly(ethylene glycol) 12000 + D-lactide (13076-17-0) → poly(D-lactide)-block-poly(ethylene glycol), Mn 14700 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

D-lactide (13076-17-0) + polyethylene glycol 20000 → poly(D-lactide)-block-poly(ethylene glycol), Mn 23100 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

D-lactide (13076-17-0) + polyethylene glycol 20000 → poly(D-lactide)-block-poly(ethylene glycol), Mn 26700 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

D-lactide (13076-17-0) + Polyethylene glycol 10000 → poly(D-lactide)-block-poly(ethylene glycol), Mn 13700 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

D-lactide (13076-17-0) + poly(ethylene glycol) 8000 → poly(D-lactide)-block-poly(ethylene glycol), Mn 11000 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

D-lactide (13076-17-0) + monomethoxypolyethylene glycol 5000 → poly(D-lactide)-block-monomethoxypoly(ethylene glycol), Mn 6900 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

D-lactide (13076-17-0) + monomethoxypolyethylene glycol 5000 → poly(D-lactide)-block-monomethoxypoly(ethylene glycol), Mn 8700 Da by NMR

Conditions	Yield
zinc at 140℃; for 168h;

L,L-dilactide (4511-42-6) + D-lactide (13076-17-0) → poly(L-lactide-b-D-lactide), DP: 52 (by 1H NMR), Mn: 7800 (by GPC), Mw/Mn: 1.07; monomer(s): L-lactide, 80 mol percent; D-lactide, 20 mol percent

Conditions	Yield
Stage #1: L,L-dilactide With calcium bis{bis(trimethylsilyl)amide} In isopropyl alcohol Stage #2: D-lactide In isopropyl alcohol

L,L-dilactide (4511-42-6) + D-lactide (13076-17-0) → poly(L-lactide-b-D-lactide), DP: 49 (by 1H NMR), Mn: 7400 (by GPC), Mw/Mn: 1.05; monomer(s): L-lactide, 66 mol percent; D-lactide, 33 mol percent

Conditions	Yield
Stage #1: L,L-dilactide With calcium bis{bis(trimethylsilyl)amide} In isopropyl alcohol Stage #2: D-lactide In isopropyl alcohol

Upstream product

• 13076-19-2 (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione 
• 4511-42-6 L,L-dilactide 
• 10326-41-7 D-Lactic acid 
• 338-69-2 D-Alanine 
• 26680-10-4 3,6-dimethyl-1,4-dioxane-2,5-dione 
• 79-33-4 L-Lactic acid 

Downstream Products

• 7699-00-5 (R)-Ethyl lactate 
• 13076-19-2 (3R,6S)-3,6-dimethyl-1,4-dioxane-2,5-dione 
• 4511-42-6 L,L-dilactide 
• 687-47-8 (S)-Ethyl lactate 
• 64231-47-6 (S)-2-hydroxy-propionic acid (S)- 1-ethoxycarbonyl-ethyl ester 
• 27871-49-4 (S)-Methyl lactate 
• 616-09-1 propyl (2R)-2-hydroxypropanoate 

Relevant articles and documents

Studies on the epimerization of diastereomeric lactides

The epimerization of chiral lactides was studied in the presence of various homogeneous and heterogeneous bases. Some solvent/base systems were found to promote epimerization at room temperature efficiently. Side reactions such as polymerization were not observed or occurred only slowly. This new protocol offers the opportunity of the transformation of meso-lactide into rac-lactide. Therefore it can reduce the overall manufacturing costs of polylactides, a problem which currently hampers the broad application of those environmentally friendly polymers in a large scale.

Preparing method of lactide stereisomer mixture

The invention provides a preparing method of a lactide stereisomer mixture, which comprises: taking an alkali metal compound as a catalyst, performing stereoisomerism reaction on a raw material lactide under a condition of 120-250 DEG C to obtain the stereisomer mixture containing D-, L- and meso- lactide, wherein the catalyst is selected from one or more from hydride, boron hydrogen compound, amide, chloride, bromide, monoiodide, sulfide, chlorate, bromate, iodate, chlorite, hypobromite, perchlorate, perbromate, periodate, sulfite, hydrosulphite, nitrate and nitrite of alkali metal. The specific alkali metal compound is taken as the catalyst for lactide isomerization reaction, the inversion of configuration of the lactide can be efficiently realized in an economic and environment-friendly manner, and the stereisomer mixture containing D-, L- and meso- lactide is prepared.

Synthesis of (R)-lactic acid and (2R,5R)-2-tert-Butyl-5-methyl-1,3-dioxolan-4-one

Abstract A convenient procedure for the synthesis of very expensive (R)-lactic acid from relatively inexpensive (R)-alanine is described. Its subsequent conversion into a chiral dioxolanone can be carried out by using an inexpensive pivalaldehyde-tert-butanol mixture.