| HS Code | 946862 |
| Product Name | Lithium Methoxide |
| Chemical Formula | CH3LiO |
| Cas Registry Number | 865-34-9 |
| Einecs Number | 212-737-3 |
| Molecular Weight | 37.97 g/mol |
| Appearance | White to off-white powder |
| Assay | 98% min |
| Density | 0.86 g/cm3 at 25 °C |
| Melting Point | >300 °C (decomposes) |
| Boiling Point | Decomposes before boiling |
| Solubility | Soluble in methanol; reacts with water |
| Flash Point | 11 °C (methanol solution) |
| Storage Conditions | Store under inert gas, dry, away from moisture |
| Hazard Classification | Corrosive; water-reactive; flammable |
| Un Number | UN 3206 |
As an accredited Lithium Methoxide factory, we enforce strict quality protocols—every batch undergoes rigorous testing to ensure consistent efficacy and safety standards.
| Packing | Lithium Methoxide supplied in 500 g UN-approved amber glass bottles, nitrogen-purged, moisture-tight, PTFE-lined caps, labeled corrosive and flammable. |
| Container Loading (20′ FCL) | 20′ FCL container loading of Lithium Methoxide, moisture-sensitive hazardous chemical, in sealed labeled packaging, compliant with IMDG and safety regulations. |
| Shipping | Lithium methoxide is shipped as a hazardous, moisture-sensitive solid under UN 3206, Class 4.2 (self-heating), subsidiary Class 8 (corrosive), Packing Group II. Use dry, sealed containers under inert gas, segregated from water, acids, oxidizers, and ignition sources, with correct labels, placards, and documentation. |
| Storage | Store lithium methoxide in a cool, dry, well-ventilated place away from heat, sparks, flames, water, acids, and oxidizers. Keep containers tightly closed under dry nitrogen or argon to prevent moisture degradation. Use an appropriate flammable-solids cabinet, ground containers during handling, and segregate from incompatible materials. Label clearly and protect containers from physical damage. |
| Shelf Life | Moisture- and air-sensitive; store sealed under inert gas in a cool, dry place. Shelf life approximately two years. |
In the synthesis of substituted cyclohexanone carboxylates and β-lactam side-chain esters, lithium methoxide is charged as a 10 wt% methanolic solution at 0.8–1.2 mol% relative to the enolizable carbonyl substrate. The substitution of sodium methoxide is implemented where residual sodium removal becomes a purification bottleneck. A glass-lined reactor with a nitrogen-blanketed jacket operating at −10 °C to +5 °C receives the lithium methoxide solution over 1.5–3.0 h through a mass-flow-controlled dosing line. After a controlled ageing period of 2–4 h, the reaction mixture is quenched with glacial acetic acid to pH 5.5–6.5, followed by vacuum distillation at a jacket temperature no greater than 45 °C to strip methanol and reduce residual solvent burden. The crude intermediate is extracted with ethyl acetate and washed with 5 wt% sodium chloride solution; phase separation in a disc-stack centrifuge at 8,000–9,000 rpm removes lithium carboxylate salts. Compliance thresholds include ICH Q3C(R8) Class 2 methanol limit of 3,000 ppm with a permitted daily exposure of 30 mg/day, and residual solvent testing is performed per USP <467>. Elemental impurity control under ICH Q3D does not currently assign a permitted daily exposure for lithium, so process validation must demonstrate lithium removal to below the analytical limit of detection of 0.5 ppm by ICP-MS before the intermediate enters downstream final API processing. Equipment-specific failure modes include methoxide precipitation in the feed line when the free methanol content falls below 85 wt% during sub-zero dosing. The terminal finished product category is advanced pharmaceutical intermediates, including cyclohexanone carboxylate esters and β-lactam side-chain synthons used in subsequent coupling steps.
For substituted pyrimidine and triazole scaffolds used as systemic fungicide precursors, lithium methoxide serves as a non-aqueous base for selective O- or N-alkylation under refluxing methanol. The reagent is charged at 1.0–1.8 mol% relative to the heterocyclic substrate, replacing potassium carbonate or cesium carbonate to reduce residual ash in the isolated intermediate. The downstream production process begins with an anhydrous methanol slurry of the heterocyclic substrate, followed by addition of lithium methoxide at 15–25 °C, then reflux at 65–70 °C for 6–12 h. Reaction progress is monitored by HPLC to confirm consumption of the starting heterocycle and suppression of dialkylated byproducts. The reaction mass is neutralized with glacial acetic acid, methanol is distilled at ≤45 °C, and the product is isolated as a crystal slurry through a Nutsche filter with a polytetrafluoroethylene cloth. Compliance is set by REACH (EC) No 1907/2006 registration dossiers and batch release under ISO 9001:2015, with residual methanol controlled below 0.5 wt% and water content below 0.2 wt% by ASTM E203-16 Karl Fischer titration. The main process incompatibility occurs when trace water in recycled methanol exceeds 500 ppm, causing lithium hydroxide formation and reduced alkylation selectivity. Terminal finished product types are substituted pyrimidines and triazole methoxy intermediates used in fungicide and herbicide synthesis, not final formulated agrochemical products.
When sodium or potassium methoxide catalysis leaves alkali-metal carryover above 10 ppm in the distilled ester, lithium methoxide is substituted at 0.2–0.6 wt% of triglyceride or ester feed in a continuous reactor system. The interchange is performed at 60–68 °C with a methanol-to-feed molar ratio of 6:1–15:1, using a static mixer upstream of a shell-and-tube reactor. The product phase is separated in a gravity decanter at 50–55 °C; the lower glycerol/methanol phase is flash-dried for methanol recovery. Residual methanol is removed in a vacuum stripping column at 80–120 mbar, followed by cation-exchange polishing to reduce lithium and sodium to <1 ppm each by ICP-OES. Compliance for the distilled methyl ester as a chemical intermediate is governed by REACH (EC) No 1907/2006; where downstream use includes engine fuels, EN 14214:2012+A2:2019 and ASTM D6751-20a limits apply. The table below summarizes the formulation gradient across three representative ester feed types.
| Ester feed type | Acid value (mg KOH/g) | LiOCH₃ addition (wt%) | Reaction temperature (°C) | Methanol:feed molar ratio | Residual Li after cation exchange (ppm) |
|---|---|---|---|---|---|
| Refined soybean oil | ≤0.5 | 0.20–0.30 | 60–62 | 6:1 | <0.5 |
| Distilled palm fatty acid distillate | 3.0–8.0 | 0.40–0.60 | 63–65 | 8:1 | <1.0 |
| Tall oil fatty acid | 5.0–12.0 | 0.55–0.70 | 64–66 | 10:1 | <1.5 |
The primary processing boundary is dissolved water in the feed: values above 200 ppm increase lithium soap formation and reduce catalyst turnover by 30–45%. Terminal finished product types are high-purity methyl esters for polymer additive intermediates, metalworking fluid base stocks, and ester-based coating additives, not commodity biodiesel.
In the preparation of lithium niobate and lithium tantalate films for electro-optic and surface acoustic wave device substrates, lithium methoxide dissolved in 2-methoxyethanol at 0.25–0.50 M is hydrolyzed with 2.0–3.0 equivalents of deionized water in a moisture-controlled glovebox maintained at ≤10 ppm H₂O. The Li:Nb molar ratio is held at 1.00 ± 0.02 to avoid lithium-deficient pyrochlore secondary phases. The solution is filtered through a 0.1 µm PTFE membrane and spin-coated onto sapphire or fused silica at 2,500–3,500 rpm for 30 s. Each layer is dried at 120–150 °C for 5 min, pyrolyzed at 350–400 °C for 15 min, and annealed at 600–700 °C under flowing oxygen in a rapid thermal annealing furnace. Film thickness increments are 80–150 nm per layer, and X-ray diffraction confirms crystallinity with a full-width at half-maximum below 0.3° 2θ for the (012) reflection. Cleanroom particle control is established under ISO 14644-1:2015 Class 5, and substrate cleaning is verified by contact angle measurement below 5° before coating. The main failure mode is crack formation when the heating ramp exceeds 10 °C/min between pyrolysis and annealing. Terminal finished product types include optical waveguides, electro-optic modulators, and surface acoustic wave filter substrates.
Lithium methoxide initiates ring-opening polymerization of ε-caprolactone in bulk at 110–140 °C under a dry nitrogen atmosphere, with a monomer-to-initiator molar ratio from 50:1 to 200:1. The target molecular weight is set by the monomer-to-initiator ratio, yielding number-average molecular weights between 8,000 g/mol and 28,000 g/mol, while polydispersity is typically ≤1.4 when conversion is kept below 85% to minimize transesterification broadening. The reaction is carried out in a 316L stainless steel stirred reactor with a magnetic drive seal, vacuum-dried at 80 °C for 2 h before charging. For L-lactide polymerization, lithium methoxide in toluene at 0.5–1.0 mol% is used at 70–80 °C; conversion is tracked by ¹H NMR integration of lactide methine protons at 5.0 ppm against polymer backbone signals. Termination is achieved with 2 M HCl in methanol, and the polymer is precipitated in cold diethyl ether. Residual lithium after precipitation is controlled below 50 ppm by repeated washing. If the final polymer is intended for implantable drug delivery matrices, the material is evaluated according to ISO 10993-1:2018; mechanical properties are characterized per ASTM D638-14 Type IV specimens cast from solution. Terminal finished product types include polycaprolactone and poly(L-lactide) matrices for controlled-release dosage forms, resorbable suture coating materials, and tissue engineering scaffolds. Published data for lithium methoxide initiation in trimethylene carbonate ring-opening is limited.
Non-aqueous metathesis routes to lithium carboxylate and sulfonate salts employ a methanolic lithium methoxide feed at 1.0–1.1 stoichiometric equivalents relative to the acid substrate at 20–35 °C. The neutralization is performed in a recirculation loop through a glass heat exchanger with a ΔT not exceeding 15 °C, using a packed column reactor to provide sufficient residence time for gas disengagement. The methanol byproduct is removed by vacuum distillation at 50–60 mbar and ≤45 °C, and the resulting lithium salt is isolated by cooling crystallization in a scraped-surface crystallizer. Residual methanol is reduced to <0.3 wt% by vacuum drying at 60 °C for 12 h. Compliance requirements for the resulting salts in electrolyte and speciality additive applications include REACH (EC) No 1907/2006 and, where exported to battery chemical specifications, customer-defined limits on moisture of <50 ppm H₂O by ASTM E203-16 Karl Fischer titration and chloride of <20 ppm by ion chromatography. The main incompatibility is exposure to carbon dioxide in ambient air, which converts lithium methoxide to lithium carbonate under closed pipeline conditions unless dry nitrogen blanketing is maintained. Terminal finished product types include lithium carboxylate salts and lithium sulfonate salts for non-aqueous electrolyte and speciality additive use.
In solution-based coating of nickel-rich layered oxide cathode precursors such as LiNi₀.₈Mn₀.₁Co₀.₁O₂, lithium methoxide is blended with transition metal nitrate or acetate solutions in methanol at a Li:transition-metal molar ratio of 1.02:1 to 1.08:1 to compensate for lithium volatilization during subsequent calcination. The precursor mixture is spray-dried in a cyclone-equipped dryer at inlet 180–220 °C and outlet 90–110 °C, then calcined in a tube furnace at 750–850 °C under flowing oxygen for 10–20 h. The spray-dried powder has a target tapped density of 1.6–2.2 g/cm³ and particle size D50 of 20–40 µm after sieve classification. Compliance with electrode-grade chemical purity is defined by concentration limits for magnetic metals of <50 ppb Fe, <20 ppb Cu, and <20 ppb Zn using ICP-MS; lithium content is verified by ICP-OES against a reference standard, and process control is maintained under ISO 9001:2015. Process limitations include the need for dew-point control below −40 °C in the spray-dryer feed area to prevent premature gelation. Terminal finished product types include lithium nickel manganese cobalt oxide cathode powders for lithium-ion cells.
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Lithium methoxide (CAS 865-34-9; LiOCH3) is supplied as a hygroscopic solid or, more commonly in industrial practice, as a methanolic solution with an active content of 10% w/w. Its molar mass is 37.97 g/mol. The methanolic solution is preferred for continuous dosing because it eliminates dust generation, reduces localized base concentration, and provides a pumpable liquid with reproducible alkalinity. Commercial product descriptions use the nomenclature “lithium methoxide in methanol” or “lithium methanolate,” with supplier-specific product codes; no universal model designation applies. The solid form is reserved for processes in which methanol cannot be tolerated and must be handled under inert gas to prevent hydrolysis and carbonation.
For methanolic solutions, vendor certificates of analysis typically report active lithium methoxide, water, sodium, carbonate, and methanol. Water content is the most process-critical parameter because water hydrolyzes the alkoxide to lithium hydroxide and methanol, reducing base strength and increasing solid precipitate formation. Published normative methods for the lithium methoxide assay itself are limited; water is normally determined by Karl Fischer titration according to ASTM E203, and methanol purity is assessed by ASTM E346. Lithium content is often measured by ICP-OES using an internal procedure because an international normative method for lithium methoxide assay is not established.
| Parameter | Representative limit | Test method |
|---|---|---|
| Lithium methoxide | 9.5–10.5% w/w | Nonaqueous acid titration |
| Water | ≤ 0.5% w/w | ASTM E203 |
| Sodium | ≤ 200 mg/kg | ICP-OES |
| Carbonate as CO32− | ≤ 0.2% w/w | Acid titration |
| Methanol | Balance | ASTM E346 |
Batch-to-batch variation in moisture and sodium content is observed most frequently in methanolic solutions stored in partially drained totes. Water uptake follows the methanol headspace rather than the liquid level alone. A tote with only 20% liquid remaining can still contain sufficient humid vapor to raise water content above 0.5% w/w after repeated open-pipe transfers if the vessel is not blanketed with dry nitrogen.
In storage and handling, the primary operational boundary is water exclusion. Solid lithium methoxide is packaged under inert gas; material transferred at relative humidity above 60% should be handled in a nitrogen-purged glovebox with a dew point of ≤ -40 °C. The solid reacts with atmospheric carbon dioxide to form lithium carbonate and releases methanol in the presence of moisture. Methanolic solutions are flammable, with a flash point near 11 °C, and require storage in grounded stainless steel or high-density polyethylene vessels away from oxidizers, chlorinated solvents, and acids. Compatibility with amine-based additives is limited because lithium methoxide can deprotonate acidic additives and generate lithium–amine complexes that change precipitation behavior. Dosing equipment typically uses 316L stainless steel or fluoropolymer-lined diaphragm pumps; carbon steel is unsuitable for extended contact with methanolic lithium methoxide service.
In biodiesel transesterification, lithium methoxide is charged at a molar ratio to oil ester bonds of 0.5 mol% to 1.5 mol%. The operating window is narrow because methanol boils at 64.7 °C, and continuous stirred-tank reactors are commonly held at 60–63 °C to balance conversion rate and vapor containment. Feedstocks with an acid number above 2 mg KOH/g typically require acid pre-esterification before base-catalyzed transesterification; otherwise methoxide is consumed by free fatty acid neutralization and soap formation becomes excessive.
Lithium soaps behave differently from sodium soaps during glycerol separation. Published comparative settling-rate data for lithium soaps in crude biodiesel are limited, but production operators commonly report denser precipitates than sodium soaps and lower tendency to stabilize emulsions than potassium soaps. Regardless of cation, residual soap must be removed by water washing or dry adsorbent treatment before fuel finishing. The final biodiesel must satisfy ASTM D6751 and EN 14214. EN 14214 limits sodium plus potassium to 5 mg/kg and calcium plus magnesium to 5 mg/kg; lithium is not directly bounded by that metal clause, but unconverted lithium soap contributes to total contamination, which is limited to 24 mg/kg in EN 14214.
On a production-scale line using a 10,000 L continuous stirred-tank reactor with a recirculation loop and static mixer, the methoxide solution is injected upstream of the static mixer. Localized high pH at the injection point can generate soap even when the bulk free fatty acid value is within specification. Delivery of the 10% w/w solution as a pre-diluted 2–3% active methanol slipstream reduces this effect. The static mixer must remain free of bypassing; insufficient pressure drop or dead zones produce heterogeneous catalyst distribution and increase batch-to-batch soap variability.
Because anionic ring-opening polymerization proceeds by chain growth that is highly sensitive to protonic impurities, lithium methoxide serves as an initiator where lithium counterion coordination influences propagation kinetics and chain-end stability. In lactide and caprolactone polymerization, the methoxide anion opens the cyclic ester at the carbonyl carbon while the lithium cation coordinates to the propagating alkoxide chain end. Residual moisture above 100 mg/kg in the monomer feed quenches active species and broadens molecular weight distribution; monomer is therefore dried to ≤ 50 mg/kg water before initiator addition. Published data for complete industrial charge specifications are limited, but batch polymerizations are typically run in jacketed glass-lined reactors with vacuum stripping at 80–90 °C before catalyst injection. Molecular weight is controlled by the monomer-to-initiator ratio. For a monomer with molar mass 100 g/mol, a 100:1 monomer-to-initiator ratio gives a theoretical number-average molecular weight of 10,000 g/mol, assuming complete initiation.
In pharmaceutical and agrochemical intermediate synthesis, lithium methoxide is used as a non-aqueous base for O-alkylation, ester cleavage, and enolate formation. The lithium cation is smaller and more Lewis acidic than sodium or potassium; it can direct the regioselectivity of enolate alkylation by chelating bidentate substrates. Stoichiometric control is critical because excess methoxide can racemize stereocenters alpha to carbonyl groups or solvolyze methyl esters. Typical use levels are 1.0–1.2 equivalents relative to the acidic substrate; additions above 1.5 equivalents are avoided unless a deliberate excess is required to drive conversion. Reactions are run in aprotic or methanolic media under inert atmosphere, with temperature maintained between -20 °C and 40 °C depending on enolate stability and alkylating agent reactivity.
Quality control in these applications relies on residual starting material and byproduct profile by GC–MS or HPLC. Because lithium methoxide is quenched with aqueous acid during workup, lithium is removed in the aqueous phase. Where the final intermediate is a pharmaceutical active ingredient, residual methanol must comply with ICH Q3C; methanol is a Class 2 solvent with a permitted daily exposure of 30.0 mg/day and a concentration limit of 3000 ppm under the standard option. This threshold frequently determines whether a solvent swap from methanol to tetrahydrofuran or 2-methyltetrahydrofuran is required after methoxide-mediated chemistry.
Lithium methoxide is selected over sodium methoxide when a less dissociated alkoxide or a lithium counterion is required. Sodium methoxide is usually supplied at 25–30% w/w in methanol, whereas lithium methoxide solutions are commonly limited to 10% w/w because of solubility constraints. The lower active concentration increases shipping volume per mole of active base but can reduce local hot spots during continuous dosing. Table 2 compares the three common methoxide bases used in transesterification and organic synthesis.
| Property | LiOCH3 | NaOCH3 | KOCH3 |
|---|---|---|---|
| Cation ionic radius | 76 pm | 102 pm | 138 pm |
| Typical methanolic solution concentration | 10% w/w | 25–30% w/w | Solid or less standardized methanol solution |
| Relative apparent base strength in methanol | Lower due to ion pairing | Intermediate | Highest |
| Soap behavior in biodiesel | Denser precipitate; limited published settling data | Waxy or gelatinous soaps | Emulsion-forming soaps |
| Preferred use | Lithium counterion chemistry, anionic polymerization | Lowest-cost methoxide base | High-activity transesterification |
The process consequences of substitution are not limited to molar cost. In transesterification, potassium methoxide reacts faster but can form potassium soaps that stabilize emulsions during glycerol separation. Sodium methoxide can produce sodium soaps that precipitate as waxy solids under cold-weather fuel processing. Lithium soaps are reported by some operators to settle more rapidly, but peer-reviewed comparative kinetic and settling-rate data are limited; a plant-scale trial should quantify residual soap mass, filter plugging tendency, and glycerol phase clarity before permanent substitution. In anionic polymerization, sodium or potassium methoxide introduces different counterion dynamics; lithium is preferred for chain-end control and reduced aggregation in cyclic ester systems.
Compared with lithium hydroxide monohydrate (CAS 1310-66-3), lithium methoxide provides non-aqueous basicity for reactions in which water cannot be tolerated. Lithium hydroxide is an inorganic base used in lubricating grease and alkaline battery applications, whereas lithium methoxide is a nucleophilic alkoxide capable of deprotonation and methylation. The choice between them is governed by the acceptable water content in the process stream and by whether methoxide incorporation into the product is intended.
Published data for the use of lithium methoxide in lithium-ion battery electrolyte precursor purification is limited; industrial practice focuses on lithium alkoxides as precursors for lithium salts and coatings because they avoid sulfate or chloride contamination when derived from lithium metal. The operational boundary is the requirement for chloride-free lithium alkoxide when downstream electrochemical stability is specified. Electrolyte-grade lithium salts commonly specify water at ≤ 50 mg/kg; methoxide feed-grade purity must be established with the supplier to ensure that alkali-metal impurities and methanol are removed by vacuum stripping after reaction with the target anion source.
