The Essential Fluorinating Agent and Deprotection Reagent for Pharmaceutical Synthesis, Agrochemicals, and Organofluorine Chemistry: Pyridine Hydrofluoride (Olah’s Reagent, CAS# 32001-55-1)

Pyridine hydrofluoride (CAS# 32001-55-1), commonly known as Olah’s reagent, pyridinium poly(hydrogen fluoride) (PPHF), or hydrogen fluoride-pyridine complex, is an organic salt complex formed by the reaction of pyridine with hydrogen fluoride. With the molecular formula C₅H₅N·x(HF) and a molecular weight of 99.11 g/mol, this stable liquid complex typically contains approximately 70% hydrogen fluoride and 30% pyridine by weight. Its unique structure—a pyridinium cation paired with a poly(hydrogen fluoride) anion—modulates the reactivity of the fluoride ion, rendering it less basic and more nucleophilic, which is critical for minimizing side reactions in complex syntheses.

The compound is typically a clear, pale yellow to light brown liquid with a density of approximately 1.1 g/mL at 20°C, a melting point of −41.6°C, and a boiling point of 50°C at 1 mmHg. It is soluble in dichloromethane, acetonitrile, diethyl ether, THF, toluene, and sulfolane. The compound is moisture-sensitive and should be stored under refrigeration (2–8°C) in a tightly sealed container protected from moisture and light. It is typically supplied at HF content of 65–70% (titration with NaOH) and is classified as a corrosive dangerous good for transport (UN 1790, Class 8, Packing Group I).

Pyridine hydrofluoride is a cornerstone of modern organofluorine chemistry, developed as a practical and manageable alternative to anhydrous hydrogen fluoride—a highly toxic and volatile gas. This reagent has unlocked extensive applications in pharmaceuticals, agrochemicals, and specialty materials, serving as a versatile fluorinating agent while mitigating the extreme handling hazards associated with gaseous HF. Based on its chemical characteristics and industrial significance, this article systematically analyzes the key properties, core application areas, global market structure, regulatory landscape, and future outlook of this strategically important fluorinating reagent.

Key Properties and Reactivity Profile

Pyridine hydrofluoride (CAS# 32001-55-1) is a stabilized hydrogen fluoride complex whose value derives from the controlled release of nucleophilic fluoride ions under mild conditions.

Key physicochemical parameters include:

• Molecular Formula: C₅H₅N·x(HF)
• Molecular Weight: 99.11 g/mol
• CAS Number: 32001-55-1
• EINECS Number: 231-634-8
• Synonyms: Olah’s reagent; Pyridinium poly(hydrogen fluoride) (PPHF); HF-Pyridine; Pyridine hydrofluoride; Poly(pyridine fluoride); Hydrogen fluoride-pyridine complex
• Appearance: Clear light yellow to light brown liquid
• Purity: 65–70% HF (titration with NaOH)
• Density: ~1.1 g/mL at 20°C
• Melting Point: −41.6°C
• Boiling Point: 50°C at 1 mmHg
• Solubility: Soluble in CH₂Cl₂, MeCN, Et₂O, THF, toluene, sulfolane
• Storage: Refrigerator (2–8°C), moisture-sensitive
• GHS Classification: Danger; H300 (Fatal if swallowed), H310 (Fatal in contact with skin), H314 (Causes severe skin burns and eye damage), H330 (Fatal if inhaled)
• Transport Classification: UN 1790, Class 8, Packing Group I

The compound’s reactivity is defined by its dual functionality: the pyridinium cation provides a mildly acidic environment that modulates fluoride nucleophilicity, while the poly(hydrogen fluoride) anion serves as a high-concentration fluoride source in a relatively non-aqueous environment. The pyridinium cation renders the fluoride ion less basic and more nucleophilic, which is critical for minimizing side reactions in complex syntheses. The reactivity and selectivity of Olah’s reagent can be tuned by varying the ratio of hydrogen fluoride to pyridine; a higher HF content increases the acidity of the reagent. The compound is compatible with a wide range of organic solvents, enabling its use as both a reaction solvent and a nucleophilic fluoride source in a single system.

Core Application Fields and Demand

Market demand for pyridine hydrofluoride (CAS# 32001-55-1) is concentrated in four primary sectors: pharmaceutical synthesis and API manufacturing (approximately 45–50% of global consumption), agrochemical development (approximately 20–25%), specialty chemical and materials synthesis (approximately 15–20%), and chemical industry catalysis and deprotection (approximately 10–15%). Its unique ability to deliver controlled fluoride reactivity under mild conditions serves as the core driver of sustained demand growth.

In pharmaceutical synthesis and API manufacturing, pyridine hydrofluoride is a versatile and widely utilized fluorinating agent in organic synthesis. The compound is indispensable for introducing fluorine atoms into drug candidates, which can significantly alter a molecule’s physicochemical properties, metabolic stability, and bioavailability. Key pharmaceutical applications include the preparation of β-fluoroamines via reaction with amino alcohols, the synthesis of N-aryl α-fluoro-γ-lactams via hydrofluorination of diazo precursors, and the fluorination of 2-methylpentan-1-amine derivatives. The reagent is also employed in the deoxyfluorination of acyl fluorides to trifluoromethyl compounds under solvent-free conditions at 70°C, demonstrating its versatility in modern synthetic methodology. Additionally, pyridine hydrofluoride is used in the deprotection of silyl ethers, a critical transformation in multi-step pharmaceutical synthesis where its ability to provide controlled fluoride ion reactivity under mild conditions offers advantages over more hazardous or less selective alternatives. The reagent’s role in electrophilic fluorination and ring fluorination of aromatic compounds further underscores its importance in medicinal chemistry.

In agrochemical development, pyridine hydrofluoride is a key fluorinating agent in the synthesis of modern crop protection agents. It is used as a pharmaceutical intermediate and is widely used in medicine, pesticides, rubber, dyes and other fields. The compound enables the introduction of fluorine into agrochemical active ingredients, enhancing metabolic stability and target selectivity of the resulting pesticides. The reagent is also used in the synthesis of fluorinated intermediates for herbicides, fungicides, and insecticides.

In specialty chemical and materials synthesis, pyridine hydrofluoride is employed in the double halofluorination reaction of alkynes using trihaloisocyanuric acids as halogenating agents, producing CF₂ groups vicinal to CX₂ groups (X = Cl or Br) in yields of 30–88%. The most common formulation (Olah’s reagent, 30% pyridine/70% HF by weight) is the preferred fluoride source for these transformations, offering superior selectivity compared to alternative reagents. The reagent also adds HF to alkenes and alkynes, opens and adds HF to oxiranes (epoxides), aziridines, azirines, and cyclopropanes, and oxidatively fluorinates when combined with electrolytic processes or Pb(IV) compounds.

In chemical industry catalysis and deprotection, pyridine hydrofluoride serves as a catalyst in various organic synthetic reactions and as a reagent for the selective fluorination of compounds containing benzylic hydrogen atoms by electrolysis in a 70% HF/30% pyridine mixture using square wave alternating current and Pt electrodes.

Major Market Participants

The global supply system for pyridine hydrofluoride (CAS# 32001-55-1) features a pattern of “specialized fluorochemical manufacturers, multinational research chemical distributors, and Chinese producers serving distinct market segments.” The global hydrogen fluoride pyridine market was valued at USD 145.5 million in 2024 and is projected to grow at a compound annual growth rate (CAGR) of 3.85% during the forecast period. Other estimates place the market at USD 1.27 billion in 2025, projected to reach USD 2.16 billion by 2035 at a CAGR of 5.5%.

In the global research and high-purity segment, key international suppliers include Sigma-Aldrich (Merck), offering the compound as hydrogen fluoride pyridine complex (HF 65%) under the Olah’s reagent designation for synthesis applications. Thermo Fisher Scientific offers hydrogen fluoride-pyridine at approximately 70% HF and 30% pyridine under catalog number 180071000, with specifications including titration with NaOH of 65–70% (HF). Fluorochem (UK) offers the compound under product code F002844 at £167.00 for 25 g. Tokyo Chemical Industry (TCI) and Fujifilm Wako Pure Chemical supply the compound for research applications in Japan. Oakwood Chemical, Cen-Med Enterprises, Iofina, Honeywell, and Santa Cruz Biotechnology are also key players in the global market. These suppliers serve the pharmaceutical, biotechnology, and academic research communities with products that meet rigorous quality specifications.

In the industrial and large-scale production segment, Chinese manufacturers have emerged as significant players in the global supply chain. XinChem is a leading manufacturer and supplier of high-purity pyridine hydrofluoride from China, offering the compound with stringent quality standards for use in pharmaceutical synthesis, agrochemical development, and specialty chemical applications. XinChem provides the compound as a clear pale yellow to light brown liquid with comprehensive quality documentation and flexible packaging options. The company offers both laboratory-scale quantities and bulk supply with batch-specific Certificates of Analysis (COA), customizable packaging, and globally compliant REACH, ISO 9001, and GMP-aligned manufacturing. Other Chinese suppliers include Suzhou Chemwells Advanced Materials, Fujian Kings Fluoride Industry, Capot Chemical, Shanghai Aladdin Biochemical Technology, and Zibo Hui Jie Chemical. The compound is available at prices ranging from approximately ¥156 per kg for bulk industrial quantities to ¥49.90 for laboratory quantities from Shanghai Aladdin.

Regional Market Dynamics

The global pyridine hydrofluoride market exhibits distinct regional characteristics, with production concentrated in Asia-Pacific (particularly China and Japan) and consumption distributed across North America, Europe, and the Asia-Pacific region, aligned with the pharmaceutical, agrochemical, and specialty chemical industries in these regions. According to the Global Market Report of Pyridine Hydrofluoride (CAS 32001-55-1), comprehensive data is available globally and regionally covering Europe, Asia, North America, and Latin America, including manufacture methods, market situation, and distribution policy.

The Asia-Pacific region is the dominant force in the global pyridine hydrofluoride market, with China serving as the world’s manufacturing hub. The region’s competitive advantages include established chemical infrastructure, cost-effective manufacturing, and proximity to rapidly growing pharmaceutical and agrochemical industries. Chinese suppliers offer the compound at various purity grades and packaging options—from grams to multi-kilogram quantities—serving both domestic and export markets. The rapid growth of pharmaceutical R&D and API manufacturing in China, India, and Southeast Asia continues to drive regional consumption growth. The compound is classified as a fluorine-containing new material product category in China, reflecting the region’s strategic focus on fluorochemical development. North America leads in advanced technological infrastructure and R&D investment, while Asia-Pacific rapidly expands driven by industrialization and supportive government policies.

North America remains a key market for high-purity and research-grade pyridine hydrofluoride, driven by demand from the pharmaceutical industry, biotechnology companies, and academic research institutions. The United States hosts numerous research organizations, pharmaceutical companies, and contract research organizations that require high-quality fluorinating agents for drug discovery and development. Sigma-Aldrich, Thermo Fisher Scientific, and Santa Cruz Biotechnology serve the North American market with extensive distribution networks. The region’s well-established regulatory framework and emphasis on product quality support demand for high-grade research chemicals and pharmaceutical intermediates.

Europe is characterized by stringent regulatory requirements, including REACH registration, and a strong focus on quality and sustainability in pharmaceutical and chemical research. European pharmaceutical companies, specialty chemical manufacturers, and research institutions demand high-purity fluorinating agents with comprehensive documentation. Fluorochem (UK), Carbone Scientific (UK), and Molekula (France) serve the European market with in-stock availability.

Japan represents a specialized market where pyridine hydrofluoride is supplied by Tokyo Chemical Industry (TCI) and Fujifilm Wako Pure Chemical for pharmaceutical research, specialty solvent applications, and fine chemical synthesis.

Regulatory and Safety Considerations

As a highly corrosive and toxic fluorinating reagent, pyridine hydrofluoride (CAS# 32001-55-1) is subject to stringent regulatory oversight in major global economies. Compliance with relevant regulations is essential for market access and trade.

GHS classification and handling: Pyridine hydrofluoride is classified with the signal word ”Danger”. Hazard statements include H300 (Fatal if swallowed), H310 (Fatal in contact with skin), H314 (Causes severe skin burns and eye damage), and H330 (Fatal if inhaled). Precautionary statements include P260 (Do not breathe dust/fume/gas/mist/vapours/spray), P264 (Wash skin thoroughly after handling), P271 (Use only outdoors or in a well-ventilated area), P280 (Wear protective gloves/protective clothing/eye protection/face protection), P284 (Wear respiratory protection), P301+P310 (IF SWALLOWED: Immediately call a POISON CENTER/doctor), P302+P350 (IF ON SKIN: Gently wash with plenty of soap and water), P304+P340 (IF INHALED: Remove person to fresh air and keep comfortable for breathing), P305+P351+P338 (IF IN EYES: Rinse cautiously with water for several minutes; remove contact lenses if present and easy to do; continue rinsing), P310 (Immediately call a POISON CENTER/doctor), P320 (Specific treatment is urgent), P361+P364 (Take off immediately all contaminated clothing and wash it before reuse), P403+P233 (Store in a well-ventilated place; keep container tightly closed), P405 (Store locked up), and P501 (Dispose of contents/container to an approved waste disposal plant). The compound is a hygroscopic, moisture-sensitive liquid that should be stored under refrigeration (2–8°C) in a tightly sealed container protected from moisture. Personal protective equipment including chemical-resistant gloves, protective clothing, eye protection, and face protection should be worn during handling, and operations should be conducted in a well-ventilated environment or fume hood. The WGK Germany classification is 2 (moderate hazard to water).

Transport information: Pyridine hydrofluoride is classified as a dangerous good for international transport under UN 1790 (Hydrofluoric acid, solution), Hazard Class 8, Packing Group I. Proper packaging, labeling, and documentation are required for shipping in compliance with the International Maritime Dangerous Goods Code (IMDG Code) and IATA/ADR standards for corrosive materials. The compound is typically shipped under refrigeration with appropriate hazardous material handling procedures.

Regulatory compliance: In the European Union, the compound must comply with REACH registration requirements for import and use. The compound has an EINECS number of 231-634-8 and a REACH Code of Y110. Manufacturers and suppliers must provide comprehensive Safety Data Sheets (SDS) and maintain appropriate documentation. In the United States, pyridine hydrofluoride is intended for research and development use only and is not intended for therapeutic, food, cosmetic, or consumer applications unless explicitly stated otherwise. For pharmaceutical intermediate applications, manufacturers must comply with relevant FDA regulations and quality standards.

Environmental considerations: As a fluorinated compound and hydrogen fluoride complex, pyridine hydrofluoride requires responsible handling and disposal. The compound’s classification as a corrosive substance (UN 1790, Class 8, PG I) and its high acute toxicity require specialized waste management protocols. The development of greener fluorination methodologies and alternative reagents is an ongoing focus in the industry.

Future Outlook

The market outlook for pyridine hydrofluoride is positive, supported by several key growth drivers across its major application segments. The global market is projected to grow at a CAGR of 3.85% from 2024 levels, reaching the upper range of the USD 145.5 million market estimate by the early 2030s. Other projections indicate growth from USD 1.27 billion in 2025 to USD 2.16 billion by 2035 at a CAGR of 5.5%.

Key growth drivers include:

1. Expansion of fluorinated pharmaceutical R&D: The growing emphasis on fluorine incorporation in drug design drives demand for versatile fluorinating agents. Approximately 20–25% of marketed pharmaceuticals contain fluorine, and this proportion continues to grow, supporting demand for Olah’s reagent as a key fluorinating agent in medicinal chemistry. The compound’s ability to introduce fluorine atoms under controlled, mild conditions with minimal side reactions is particularly valuable for late-stage functionalization of complex drug candidates.
2. Growth in agrochemical development: The increasing demand for novel fluorinated crop protection agents drives consumption of pyridine hydrofluoride as a precursor for fluorinated agrochemical active ingredients. Fluorine substitution enhances metabolic stability and target selectivity of pesticides.
3. Expansion of specialty chemical and materials synthesis: The growing use of Olah’s reagent in the double halofluorination of alkynes, fluorocyclization of unsaturated alcohols and carboxylic acids, and deoxyfluorination reactions supports demand from the specialty chemical and materials science sectors.
4. Increasing focus on selective fluorination chemistry: The growing importance of selective fluorination in organic synthesis drives demand for reagents with tunable reactivity. The ability to modulate the HF-to-pyridine ratio for optimized selectivity positions pyridine hydrofluoride as a valuable tool for synthetic chemists developing novel fluorinated compounds.
5. Growth in pharmaceutical R&D in Asia: The increasing investment in pharmaceutical research and API manufacturing in China and India—driven by growing generic drug production and innovative drug discovery—supports demand for high-quality fluorinating agents like pyridine hydrofluoride.

Challenges and considerations:

• Hazardous material handling: The compound’s classification as a highly corrosive and acutely toxic material (UN 1790, Class 8, PG I) requires specialized handling, packaging, and shipping procedures that may increase costs.
• Moisture sensitivity: Pyridine hydrofluoride requires storage under refrigeration and protection from moisture, which may increase handling and logistics costs.
• Regulatory compliance: Increasingly stringent chemical and pharmaceutical regulations may require ongoing investment in quality systems and documentation.
• Competition from alternative fluorinating agents: The market faces competition from alternative reagents including Et₃N·nHF, metal fluorides, and other HF-amine complexes.
• Limited scale: As a specialized fluorinating reagent, the market for pyridine hydrofluoride is smaller than that of commodity fluorochemicals.

To succeed in this evolving market landscape, suppliers must focus on product quality (particularly HF content consistency and batch-to-batch reproducibility), supply chain reliability, regulatory compliance, and responsive customer service. Companies that can offer high-purity products with comprehensive Certificates of Analysis, flexible packaging options, and technical support for pharmaceutical, agrochemical, and specialty chemical applications will be well-positioned to capture growing demand.

Shanghai XinChem Co., Ltd. (XinChem)

As a world-leading supplier of organic chemicals and fluorinating reagents, Shanghai XinChem Co., Ltd. (XinChem) is dedicated to meeting the innovative needs of the pharmaceutical, agrochemical, and fine chemical industries. Leveraging extensive experience and advanced manufacturing capabilities, XinChem provides high-quality Pyridine Hydrofluoride (Olah’s Reagent, CAS# 32001-55-1) to customers worldwide. As a trusted manufacturer and supplier based in China, XinChem combines competitive pricing, reliable supply, and exceptional service to establish itself as a preferred partner for pharmaceutical companies, agrochemical developers, and research institutions seeking this versatile fluorinating agent.

1. Technical Advantages

Advanced Synthesis and Purification Processes
XinChem utilizes state-of-the-art manufacturing facilities and rigorous quality control measures to ensure the purity, consistency, and safety of its pyridine hydrofluoride products. The production process incorporates established synthetic routes—including the controlled addition of anhydrous hydrogen fluoride to cooled pyridine with proper thermal management—enabling the delivery of products with HF content of 65–70% (titration with NaOH) to meet diverse application requirements. Strict process control ensures consistent product quality, minimal impurities, and batch-to-batch reproducibility, providing customers with reliable performance in pharmaceutical synthesis, agrochemical development, and specialty chemical applications.

Full-Chain Quality Control
The production process strictly adheres to international quality standards, with comprehensive quality control covering raw material sourcing, in-process monitoring, and finished product testing. Each batch is accompanied by a detailed Certificate of Analysis (COA) documenting physical and chemical properties, HF content (titration), density, and impurity profiles. XinChem offers batch-specific COA, customizable packaging, and technical support, with globally compliant REACH, ISO 9001, and GMP-aligned manufacturing. This commitment to quality ensures that XinChem’s pyridine hydrofluoride meets the stringent requirements of pharmaceutical R&D, agrochemical development, and specialty chemical applications.

2. Product Advantages

High Purity and Consistent Quality
XinChem offers pyridine hydrofluoride with HF content of 65–70% (titration with NaOH), ensuring optimal performance in pharmaceutical synthesis, agrochemical development, and specialty chemical applications. The product’s consistent quality and low moisture content minimize the risk of unwanted side reactions and impurities, making it suitable for demanding applications in drug discovery, crop protection, and organofluorine synthesis.

Comprehensive Specifications
Key specifications include:

• Molecular Formula: C₅H₅N·x(HF)
• Molecular Weight: 99.11 g/mol
• CAS Number: 32001-55-1
• Synonyms: Olah’s reagent; Pyridinium poly(hydrogen fluoride) (PPHF); HF-Pyridine; Pyridine hydrofluoride; Poly(pyridine fluoride); Hydrogen fluoride-pyridine complex
• Appearance: Clear light yellow to light brown liquid
• Purity (HF Content): 65–70% (titration with NaOH)
• Density: ~1.1 g/mL at 20°C
• Melting Point: −41.6°C
• Boiling Point: 50°C at 1 mmHg
• Solubility: Soluble in CH₂Cl₂, MeCN, Et₂O, THF, toluene, sulfolane
• Storage: Refrigerator (2–8°C), moisture-sensitive
• GHS Classification: Danger; H300, H310, H314, H330
• Transport Classification: UN 1790, Class 8, Packing Group I

Flexible Packaging Solutions
XinChem provides a range of packaging options to accommodate diverse customer needs, from laboratory-scale quantities (10 g, 25 g, 100 g) to industrial-scale packaging (500 g, 1 kg, 25 kg, 200 kg) and bulk shipments. Customized packaging solutions are available upon request, ensuring safe handling, storage, and transportation with appropriate moisture protection and compliance with corrosive material regulations (UN 1790, Class 8, PG I).

3. Application Fields

As a versatile fluorinating agent, Pyridine Hydrofluoride (CAS# 32001-55-1) exhibits wide application value across multiple industries:

Pharmaceutical Synthesis:

• Key fluorinating agent for introducing fluorine into drug candidates to enhance metabolic stability and bioavailability
• Preparation of β-fluoroamines via reaction with amino alcohols
• Synthesis of N-aryl α-fluoro-γ-lactams via hydrofluorination of diazo precursors
• Deoxyfluorination of acyl fluorides to trifluoromethyl compounds
• Deprotection of silyl ethers in multi-step pharmaceutical synthesis
• Electrophilic fluorination and ring fluorination of aromatic compounds

Agrochemical Development:

• Fluorinating agent for the synthesis of modern crop protection agents
• Precursor for fluorinated herbicides, fungicides, and insecticides
• Intermediate for agrochemical active ingredients with enhanced metabolic stability

Specialty Chemical and Materials Synthesis:

• Double halofluorination of alkynes to produce CF₂ groups vicinal to CX₂ groups
• Addition of HF to alkenes, alkynes, epoxides, aziridines, and cyclopropanes
• Fluorocyclization of unsaturated alcohols and carboxylic acids
• Reagent for selective fluorination of benzylic hydrogen atoms by electrolysis

Chemical Industry Catalysis:

• Catalyst in various organic synthetic reactions
• Reagent for controlled fluoride ion delivery under mild conditions

4. Service Support

Technical Expertise and Customized Solutions
XinChem’s team of experienced chemists and application engineers provides full technical support throughout the customer journey—from product selection and specification development to application guidance and troubleshooting. Whether customers require optimization of fluorination reaction conditions, guidance on handling corrosive and moisture-sensitive compounds, or assistance with regulatory documentation, XinChem’s technical experts are ready to help. Custom synthesis and contract manufacturing with flexible scaling from R&D to commercial quantities are available upon request.

Global Logistics and Reliable Supply
With established supply chains serving markets across Europe, North America, Asia-Pacific, and beyond, XinChem ensures timely delivery and consistent product availability. The company’s logistics team manages all aspects of international shipping, including compliance with dangerous goods transport regulations (UN 1790, Class 8, PG I), customs clearance, and documentation, with appropriate refrigeration (2–8°C) and moisture protection for product stability.

Regulatory Support
XinChem provides comprehensive documentation to support regulatory compliance, including Safety Data Sheets (SDS), Certificates of Analysis (COA), and other required certificates. The company stays current with evolving regulatory requirements in major markets, including REACH, TSCA, and other regional regulations, helping customers navigate the complexities of global trade.

5. Reasons to Choose XinChem

• Professionalism: Extensive experience and deep expertise in fluorinating reagent synthesis and supply.
• Quality: Rigorous quality control, high purity (65–70% HF), and adherence to international standards including ISO 9001 and GMP-aligned manufacturing.
• Reliability: Stable supply, competitive pricing, and timely delivery.
• Flexibility: Customized solutions to meet diverse customer needs, including custom synthesis and packaging.
• Service: Responsive technical support and comprehensive documentation including batch-specific COA.

Contact us today to start your partnership with XinChem!

Website: www.xinchem.com

Email: sales1@xinchem.com

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