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Guidance for Industry Q3C Tables and List U.S. Department of Health and Human Services Food and Drug Administration Center for Drug Evaluation and Research (CDER) Center for Biologics Evaluation and Research (CBER) February 2012 ICH Revision 2

Guidance for Industry Q3C Tables and List Additional copies are available from: Office of Communications Division of Drug Information, WO51, Room 2210 Center for Drug Evaluation and Research Food and Drug Administration 10903 New Hampshire Ave. Silver Spring, MD 20993 Phone: 301-796-3400; Fax: 301-847-8714 druginfo@fda.hhs.gov http://www.fda.gov/drugs/guidancecomplianceregulatoryinformation/guidances/default.htm and/or Office of Communication, Outreach and Development, HFM-40 Center for Biologics Evaluation and Research Food and Drug Administration 1401 Rockville Pike, Rockville, MD 20852-1448 http://www.fda.gov/biologicsbloodvaccines/guidancecomplianceregulatoryinformation/guidances/default.htm (Tel) 800-835-4709 or 301-827-1800 U.S. Department of Health and Human Services Food and Drug Administration Center for Drug Evaluation and Research (CDER) Center for Biologics Evaluation and Research (CBER) February 2012 ICH Revision 2

Guidance for Industry 1 Q3C Tables and List This guidance represents the Food and Drug Administration's (FDA s) current thinking on this topic. It does not create or confer any rights for or on any person and does not operate to bind FDA or the public. You can use an alternative approach if that approach satisfies the requirements of the applicable statutes and regulations. If you want to discuss an alternative approach, contact the FDA staff responsible for implementing this guidance. If you cannot identify the appropriate FDA staff, call the appropriate number listed on the title page of this guidance. I. INTRODUCTION This is the companion document for the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH) guidance for industry Q3C Impurities: Residual Solvents (1997), which makes recommendations as to what amounts of residual solvents are considered safe in pharmaceuticals. This document may be updated if proposals for change are submitted to the International Conference on Harmonisation (ICH) Steering Committee. Proposals for change and the ICH Steering Committee final decision on any proposed changes will be announced through a notice in the Federal Register prior to the updating of this document. The guidance was revised in November 2003 to reflect updated recommendations for N-Methylpyrrolidone and Tetrahydrofuran and in February 2012 to reflect an updated recommendation for cumene. FDA s guidance documents, including this guidance, do not establish legally enforceable responsibilities. Instead, guidances describe the Agency's current thinking on a topic and should be viewed only as recommendations, unless specific regulatory or statutory requirements are cited. The use of the word should in Agency guidances means that something is suggested or recommended, but not required. 1 This document was developed within the Expert Working Group (Quality) of the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH) and has been subject to consultation by the regulatory parties, in accordance with the ICH process. This document was endorsed by the ICH Steering Committee at Step 4 of the ICH process in July 1997. At Step 4 of the process, the final draft is recommended for adoption to the regulatory bodies of the European Union, Japan, and the United States. This guidance was published in the Federal Register on December 24, 1997 (62 FR 67377), and is applicable to drug and biological products. 1

II. LIST OF SOLVENTS INCLUDED IN THE Q3C GUIDANCE Solvent Other Names Structure Class Acetic acid Acetone Acetonitrile Ethanoic acid 2-Propanone Propan-2-one CH 3 COOH Class 3 CH 3 COCH 3 Class 3 CH 3 CN Anisole Methoxybenzene Class 3 Benzene Benzol Class 1 1-Butanol 2-Butanol Butyl acetate tert-butylmethyl ether Carbon tetrachloride Chlorobenzene n-butyl alcohol Butan-1-ol sec-butyl alcohol Butan-2-ol Acetic acid butyl ester 2-Methoxy-2-methyl-propane Tetrachloromethane CH 3 (CH 2 ) 3 OH Class 3 CH 3 CH 2 CH(OH)CH 3 Class 3 CH 3 COO(CH 2 ) 3 CH 3 Class 3 (CH 3 ) 3 COCH 3 Class 3 CCl 4 Class 1 Chloroform Cumene Cyclohexane Trichloromethane Isopropylbenzene (1-Methyl)ethylbenzene Hexamethylene CHCl 3 C 6 H 5 -CH(CH 3 ) 2 1,2-Dichloroethane 1,1-Dichloroethene 1,2-Dichloroethene sym-dichloroethane Ethylene dichloride Ethylene chloride 1,1-Dichloroethylene Vinylidene chloride 1,2-Dichloroethylene Acetylene dichloride 2 CH 2 ClCH 2 Cl Class 1 H 2 C=CCl 2 Class 1 ClHC=CHCl

Dichloromethane Methylene chloride CH 2 Cl 2 1,2-Dimethoxyethane Ethyleneglycol dimethyl ether Monoglyme Dimethyl Cellosolve H 3 COCH 2 CH 2 OCH 3 N,N- Dimethylacetamide N,N- Dimethylformamide Dimethyl sulfoxide 1,4-Dioxane DMA DMF Methylsulfinylmethane Methyl sulfoxide DMSO p-dioxane [1,4]Dioxane CH 3 CON(CH 3 ) 2 HCON(CH 3 ) 2 (CH 3 ) 2 SO Class 3 Ethanol 2-Ethoxyethanol Ethyl acetate Ethyleneglycol Ethyl ether Ethyl formate Formamide Formic acid Heptane Hexane Isobutyl acetate Isopropyl acetate Methanol 2-Methoxyethanol Methyl acetate 3-Methyl-1-butanol Ethyl alcohol Cellosolve Acetic acid ethyl ester 1,2-Dihydroxyethane 1,2-Ethanediol Diethyl ether Ethoxyethane 1,1 -Oxybisethane Formic acid ethyl ester Methanamide n-heptane n-hexane Acetic acid isobutyl ester Acetic acid isopropyl ester Methyl alcohol Methyl Cellosolve Acetic acid methyl ester Isoamyl alcohol Isopentyl alcohol 3-Methylbutan-1-ol CH 3 CH 2 OH Class 3 CH 3 CH 2 OCH 2 CH 2 OH CH 3 COOCH 2 CH 3 Class 3 HOCH 2 CH 2 OH CH 3 CH 2 OCH 2 CH 3 Class 3 HCOOCH 2 CH 3 Class 3 HCONH 2 HCOOH Class 3 CH 3 (CH 2 ) 5 CH 3 Class 3 CH 3 (CH 2 ) 4 CH 3 CH 3 COOCH 2 CH(CH 3 ) 2 Class 3 CH 3 COOCH(CH 3 ) 2 Class 3 CH 3 OH CH 3 OCH 2 CH 2 OH CH 3 COOCH 3 Class 3 (CH 3 ) 2 CHCH 2 CH 2 OH Class 3 3

Methylbutyl ketone 2-Hexanone Hexan-2-one CH 3 (CH 2 ) 3 COCH 3 Methylcyclohexane Cyclohexylmethane Methylethyl ketone Methylisobutyl ketone 2-Butanone MEK Butan-2-one 4-Methylpentan-2-one 4-Methyl-2-pentanone MIBK CH 3 CH 2 COCH 3 CH 3 COCH 2 CH(CH 3 ) 2 Class 3 Class 3 2-Methyl-1-propanol N-Methylpyrrolidone Isobutyl alcohol 2-Methylpropan-1-ol 1-Methylpyrrolidin-2-one 1-Methyl-2-pyrrolidinone (CH 3 ) 2 CHCH 2 OH Class 3 Nitromethane CH 3 NO 2 Pentane n-pentane CH 3 (CH 2 ) 3 CH 3 Class 3 1-Pentanol 1-Propanol 2-Propanol Amyl alcohol Pentan-1-ol Pentyl alcohol Propan-1-ol Propyl alcohol Propan-2-ol Isopropyl alcohol CH 3 (CH 2 ) 3 CH 2 OH Class 3 CH 3 CH 2 CH 2 OH Class 3 (CH 3 ) 2 CHOH Class 3 Propyl acetate Acetic acid propyl ester CH 3 COOCH 2 CH 2 CH 3 Class 3 Pyridine Sulfolane Tetrahydrothiophene 1,1-dioxide Tetrahydrofuran Tetramethylene oxide Oxacyclopentane Tetralin 1,2,3,4-Tetrahydro-naphthalene Toluene Methylbenzene 1,1,1-Trichloroethane Methylchloroform CH 3 CCl 3 Class 1 1,1,2-Trichloroethene Trichloroethene HClC=CCl 2 Xylene 1 Dimethybenzene Xylol 4

1 Usually 60% m-xylene, 14% p-xylene, 9% o-xylene with 17% ethyl benzene. III. SOLVENTS GROUPED BY CLASS Solvents in Class 1 (Table 1) should not be employed in the manufacture of drug substances, excipients, and drug products because of their unacceptable toxicity or their deleterious environmental effect. However, if their use is unavoidable in order to produce a drug product with a significant therapeutic advance, then their levels should be restricted as shown in Table 1, unless otherwise justified. The solvent 1,1,1-Trichloroethane is included in Table 1 because it is an environmental hazard. The stated limit of 1,500 ppm is based on a review of the safety data. Table 1. Class 1 Solvents in Pharmaceutical Products (Solvents That Should Be Avoided) Solvent Concentration Limit (ppm) Concern Benzene 2 Carcinogen Carbon tetrachloride 4 Toxic and environmental hazard 1,2-Dichloroethane 1,1-Dichloroethene 1,1,1-Trichloroethane 5 8 1,500 Toxic Toxic Environmental hazard 5

Solvents in (Table 2) should be limited in pharmaceutical products because of their inherent toxicity. PDEs are given to the nearest 0.1 mg/day, and concentrations are given to the nearest 10 ppm. The stated values do not reflect the necessary analytical precision of determination. Precision should be determined as part of the validation of the method. Table 2. Solvents in Pharmaceutical Products Solvent PDE (mg/day) Concentration Limit (ppm) Acetonitrile 4.1 410 Chlorobenzene 3.6 360 Chloroform 0.6 60 Cyclohexane 38.8 3,880 Cumene 0.7 70 1,2-Dichloroethene 18.7 1,870 Dichloromethane 6.0 600 1,2-Dimethoxyethane 1.0 100 N,N-Dimethylacetamide 10.9 1,090 N,N-Dimethylformamide 8.8 880 1,4-Dioxane 3.8 380 2-Ethoxyethanol 1.6 160 Ethyleneglycol 6.2 620 Formamide 2.2 220 Hexane 2.9 290 Methanol 30.0 3,000 2-Methoxyethanol 0.5 50 Methylbutyl ketone 0.5 50 Methylcyclohexane 11.8 1,180 N-Methylpyrrolidone 5.3 530 Nitromethane 0.5 50 Pyridine 2.0 200 Sulfolane 1.6 160 Tetrahydrofuran 7.2 720 Tetralin 1.0 100 Toluene 8.9 890 1,1,2-Trichloroethene 0.8 80 Xylene 1 21.7 2,170 1 Usually 60% m-xylene, 14% p-xylene, 9% o-xylene with 17% ethyl benzene. 6

Solvents in Class 3 (Table 3) may be regarded as less toxic and of lower risk to human health. Class 3 includes no solvent known as a human health hazard at levels normally accepted in pharmaceuticals. However, there are no long-term toxicity or carcinogenicity studies for many of the solvents in Class 3. Available data indicate that they are less toxic in acute or short-term studies and negative in genotoxicity studies. It is considered that amounts of these residual solvents of 50 mg per day or less (corresponding to 5,000 ppm or 0.5 percent under Option 1) would be acceptable without justification. Higher amounts may also be acceptable provided they are realistic in relation to manufacturing capability and good manufacturing practice (GMP). Table 3. Class 3 Solvents Which Should Be Limited by GMP or Other Quality-Based Requirements Acetic acid Acetone Anisole 1-Butanol 2-Butanol Butyl acetate tert-butylmethyl ether Dimethyl sulfoxide Ethanol Ethyl acetate Ethyl ether Ethyl formate Formic acid Heptane Isobutyl acetate Isopropyl acetate Methyl acetate 3-Methyl-1-butanol Methylethyl ketone Methylisobutyl ketone 2-Methyl-1-propanol Pentane 1-Pentanol 1-Propanol 2-Propanol Propyl acetate 7

The solvents listed in Table 4 may also be of interest to manufacturers of excipients, drug substances, or drug products. However, no adequate toxicological data on which to base a PDE were found. Manufacturers should supply justification for residual levels of these solvents in pharmaceutical products. Table 4. Solvents for Which No Adequate Toxicological Data Were Found 1,1-Diethoxypropane 1,1-Dimethoxymethane 2,2-Dimethoxypropane Isooctane Isopropyl ether Methylisopropyl ketone Methyltetrahydrofuran Petroleum ether Trichloroacetic acid Trifluoroacetic acid 8