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Spontaneous Symmetry Breaking in Polar Fluids
Calum Gibb ; Jordan Hobbs ; Diana Nikolova ; Tom Raistrick ; Helen Gleeson ; Richard Mandle
Abstract: Spontaneous symmetry breaking and emergent polar order are each of fundamental importance to a range of scientific disciplines, as well as generating rich phase behaviour in liquid crystals (LCs). Here, we show the union of these phenomena to lead to two previously undiscovered polar liquid states of matter. Both phases have a lamellar structure with an inherent polar ordering of their constituent molecules. The first of these phases is characterised by polar order and a local tilted structure; the tilt direction precesses about a helix orthogonal to the layer normal, the period of which is such that we observe selective reflection of light. The second new phase type is anti-ferroelectric, with the constituent molecules aligning orthogonally to the layer normal. This has led us to term the phases the SmC_P^H and SmAAF phases, respectively. Further to this, we obtain room temperature ferroelectric nematic (NF) and SmC_P^Hphases via binary mixture formulation of the novel materials described here with a standard NF compound (DIO), with the resultant materials having melting points (and/or glass transitions) which are significantly below ambient temperature.
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CAS No. : | 269409-70-3 |
Formula : | C12H17BO3 |
M.W : | 220.07 |
SMILES Code : | OC1=CC=C(B2OC(C)(C)C(C)(C)O2)C=C1 |
MDL No. : | MFCD02093756 |
InChI Key : | BICZJRAGTCRORZ-UHFFFAOYSA-N |
Pubchem ID : | 2734624 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | at 80℃; Sealed tube | In a sealed tube was added 2-hydroxy-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)pyridine (300 mg, 1.357 mmol), sodium chlorodifluoroacetate (320 mg, 2.036 mmol) in acetonitrile (5 mL). This suspension was heated to 80°C and stirred overnight. The reaction mixture was cooled down to rt, diluted with EtOAc, washed with an aqueous solution of NaHC03 and brine. The organic layer dried over MgS04, filtered and evaporated. Purification by flash chromatography on silica gel (CH2CI2/MeOH, 95/5) gave the title compound (197 mg, 53percent yield). MS: 272.8 [M+H]+, Rt (6) = 3.12 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate;palladium diacetate; triphenylphosphine; In 1,4-dioxane; water; at 60℃; for 1h; | 2d) Methyl 7-[4-([3-(2,6-dichlorophenyl)-5-(1-methylethyl)-4-isoxazolyl]methyl}oxy)phenyl]-3-quinolinecarboxylate A solution of 78 mg (0.29 mmol) of <strong>[1001756-23-5]methyl 7-bromo-3-quinolinecarboxylate</strong>, 97 mg (0.44 mmol) of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol, 3 mg (0.01 mmol) of palladium acetate, 8 mg (0.03 mmol) of triphenylphosphine, 218 mg (1.03 mmol) of K3PO4 and 25 muL of H2O in 1.0 mL of dioxane was stirred at 60° C. for 1 hr. EtOAc was added and the organics were washed with water and brine then concentrated. To the residue was added 65 mg (0.21 mmol) of 4-(chloromethyl)-3-(2,6-dichlorophenyl)-5-(1-methylethyl)isoxazole, 74 mg (0.54 mmol) of K2CO3 and 1.5 mL of DMF and the mixture was then stirred at 60° C. for 1 hr. EtOAc was added and the organics were washed with three portions of water, then brine. The solution was concentrated and the residue purified by silica gel chromatography (12 g of silica gel eluding with 0-40percent EtOAc in hexanes over 45 minutes) to give 47 mg (30percent) of methyl 7-[4-([3-(2,6-dichlorophenyl)-5-(1-methylethyl)-4-isoxazolyl]methyl}oxy)phenyl]-3-quinolinecarboxylate as a clear glass. 1H NMR (400 MHz, CDCl3): delta 9.44 (s, 1H), 8.83 (s, 1H), 8.28 (s, 1H), 7.96 (d, J=9 Hz, 1H), 7.82 (d, J=9 Hz, 1H), 7.64 (d, J=9 Hz, 2H), 7.41 (d, J=8 Hz, 2H), 7.35-7.31 (m, 1H), 6.92 (d, J=9 Hz, 2H), 4.79 (s, 2H), 4.02 (s, 3H), 3.38-3.34 (m, 1H), 1.45 (d, J=7 Hz, 6H). ESI-LCMS m/z 548 (M+H)+. | |
With potassium phosphate; palladium diacetate; triphenylphosphine; In 1,4-dioxane; water; at 60℃; for 1h; | A solution of <strong>[1001756-23-5]methyl 7-bromo-3-quinolinecarboxylate</strong> 2c (78 mg, 0.29 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol 3b (97 mg, 0.44 mmol), palladium(II) acetate (3 mg, 0.01 mmol), triphenylphosphine (8 mg, 0.03 mmol), potassium phosphate (218 mg, 1.03 mmol), and water (25 muL) in dioxane (1.0 mL) was stirred at 60 °C for 1 hour. Ethyl acetate was added and the organics were washed with water and brine, and then concentrated to give methyl 7-(4-hydroxyphenyl)quinoline-3-carboxylate 4c. To methyl 7-(4-hydroxyphenyl)quinoline-3-carboxylate 4c was added 4-(chloromethyl)-3-(2,6-dichlorophenyl)-5-(1-methylethyl)isoxazole 5a (65 mg, 0.21 mmol), potassium carbonate (74 mg, 0.54 mmol) and N,N-dimethylformamide (1.5 mL) and the mixture was then stirred at 60 °C for 1 hour. Ethyl acetate was added and the organics were washed with three portions of water, then brine. The solution was concentrated, and the residue was purified by silica gel chromatography (hexanes to 2:3 ethyl acetate:hexanes) to give methyl 7-[4-([3-(2,6-dichlorophenyl)-5-(1-methylethyl)-4-isoxazolyl]methyl}oxy)phenyl]-3-quinolinecarboxylate (47 mg, 30percent) as a clear glass (1H NMR (400 MHz, CDCl3): 9.44 (s, 1H), 8.83 (s, 1H), 8.28 (s, 1H), 7.96 (d, J = 9 Hz, 1H), 7.82 (d, J = 9 Hz, 1H), 7.64 (d, J = 9 Hz, 2H), 7.41 (d, J = 8 Hz, 2H), 7.35-7.31 (m, 1H), 6.92 (d, J = 9 Hz, 2H), 4.79 (s, 2H), 4.02 (s, 3H), 3.38-3.34 (m, 1H), 1.45 (d, J = 7 Hz, 6H); ESI-LCMS m/z 548 (M+H)). To methyl 7-[4-([3-(2,6-dichlorophenyl)-5-(1-methylethyl)-4-isoxazolyl]methyl}oxy)phenyl]-3-quinolinecarboxylate (47 mg, 0.09 mmol) in a mixture of ethanol (3 mL), tetrahydrofuran (1 mL), and water (1 mL) was added sodium hydroxide (35 mg, 0.86 mmol) and the mixture stirred at 50 °C for 16 hours. The mixture was concentrated to 1/3 volume then added dropwise to a stirred solution of 0.5 N hydrochloric acid (10 mL). The resulting solids were collected by suction filtration, washed with water, then dried to yield 7-[4-([3-(2,6-dichlorophenyl)-5-(1-methylethyl)-4-isoxazolyl]methyl}oxy)phenyl]-3-quinolinecarboxylic acid 1e (32 mg, 70percent) as a yellow solid. 1H NMR (400 MHz, DMSO-d6): delta 9.30 (s, 1H), 8.97 (s, 1H), 8.24-8.21 (m, 2H), 7.99 (d, J = 8 Hz, 1H), 7.76 (d, J = 8 Hz, 2H), 7.63-7.61 (m, 2H), 7.55-7.52 (m, 1H), 6.93 (d, J = 9 Hz, 2H), 4.88 (s, 2H), 3.50-3.44 (septet, J = 7 Hz, 1H), 1.33 (d, J = 7 Hz, 6H); ESI-LCMS m/z 534 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; for 5h;Heating / reflux; | Example 1 Compound (1) is prepared as follows : Step 1.1 : 2. 5'-Bis (4-hvdroxyphenYl) bithiophene.; To a solution of 5, 5'-dibromo-2, 2'-bithiophene (5.0 g, 15.43 mmol) in anhydrous THF (120 ml) is added tetrakis (triphenylphosphine) palladium (0.5 g, 0.43 mmol). This mixture is degassed with nitrogen for 20 min, followed by the addition of 4- (4, 4,5, 5-tetramethyl [1, 3,2] dioxoborolan-2-yl)-phenol (3.73 g, 16.95 mmol, Aldrich) and tetraethylamomnium hydroxide (20% solution in water, 50 ml). The mixture is heated at reflux for 5 h. After cooling, 1 M HCI solution (70 mt) is added and the precipitate is filtered off then washed with water (3 x 20 ml) and dried, to give a green solid (4.52 g, 84 %). NMR showed the expected signals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With caesium carbonate; In N,N-dimethyl-formamide; at 100.0℃; | Compound 5d: A mixture of compound 6 (2.1 g, 10.9 mmol), compound 7 (2.4g, 10.9 mmol) and Cs2C03 (3.5 g, 10.9 mmol) in DMF (14 mL) was heated at 100C for 4 hours. After cooling to room temperature, the mixture was filtered through a plug of silica gel and the plug was washed with EtOAc (50 mL). The filtrate was concentrated and the residue was purified by column chromatography (40 g silica gel, 0-30% EtOAc/Hexane) to obtain compound 5d (2.3 g, 6.9 mmol). 1H NMR (400MHz, CD3OD): 7.81 (d, 2H, J=8.8Hz), 7.63 (d, 1H, J=8.8Hz), 7.26 (d, 1H, J=2.4Hz), 7.17 (dd, 1H, Jl=2.4, J2=8.8Hz), 6.98 (d, 2H, J=8.8Hz), 1.28 (s, 12H). | |
2.3 g | With caesium carbonate; In N,N-dimethyl-formamide; at 100.0℃; for 4.0h; | [0323] (c) Compound 12 was prepared as follows:[0324] A mixture of compound 16 (2.1 g, 10.9 mmol), compound 17 (2.4g, 10.9 mmol) and Cs2C03 (3.5 g, 10.9 mmol) in DMF (14 mL) was heated at 100C for 4 hours. After cooling to room temperature, the mixture was filtered through a plug of silica gel and the plug was washed with EtOAc (50 mL). The filtrate was concentrated and the residue was purified by column chromatography (40 g silica gel, 0-30% EtOAc/Hexane) to obtain compound 12 (2.3 g, 6.9 mmol). ? NMR (400MHz, CD3OD): ? 7.81 (d, 2H, J=8.8Hz), 7.63 (d, 1H, J=8.8Hz), 7.26 (d, 1H, J=2.4Hz), 7.17 (dd, 1H, Jl=2.4, J2=8.8Hz), 6.98 (d, 2H, J=8.8Hz), 1.28 (s, 12H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27% | With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0 - 25℃; for 18h;Inert atmosphere; | l-[3-[4-(4,4,5,5-Tetramethyl-l,3,2-dioxaborolan-2-yl)phenoxy]propyl]pyrrolidine can also be prepared as follows: Diisopropylazodicarboxylate (6.71 mL, 34.08 mmol) was added dropwise to 4-(4,4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)phenol (5.00 g, 22.72 mmol), triphenylphosphine (8.94 g, 34.08 mmol) and 3-(pyrrolidin-l-yl)propan-l-ol (4.40 g, 34.08 mmol) in THF (50 mL) at 0°C under nitrogen. The resulting mixture was allowed to warm up to room temperature and stirred for 18 h. The reaction mixture was evaporated to afford yellow oil. The yellow oil was triturated from heptane/EtOAc (80/20), and the white solid was filtered off. The filtrate was concentrated and the crude product was purified by FCC, elution gradient 0 to 100percent EtOAc in heptane. Pure fractions were evaporated to dryness to afford the desired material as a pale yellow gum (2.05 g, 27 percent>). 'H NMR (500MHz, DMSO-d6) delta 1.13 (2H, t), 1.28 (12H, s), 1.68 (4H, dq), 1.79 - 1.96 (2H, m), 2.46 - 2.56 (4H, m), 3.94 - 4.11 (2H, m), 6.83 - 6.97 (2H, m), 7.58 - 7.66 (2H, m). Mass Spectrum: m/z (ES+)[M+H]+ not observed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With diamide; triphenylphosphine; In tetrahydrofuran; at 20℃; for 24h;Inert atmosphere; | To a solution of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (a) (82.7 g, 364.51 mmol) in THF (2 L) was added under argon (R)-1-N-Boc-3-hydroxypyrrolidine (b) (84.43 g, 437.41 mmol) followed by N,N,N′,N′-tetramethylazodicarboxamide (99.1 g, 546.77 mmol). The clear reaction mixture turned orange and triphenylphosphine (143.41 g, 546.77 mmol) was added. The reaction mixture was stirred at room temperature for 24 hours, meanwhile a precipitate of triphenylphosphine oxide formed (Ph3P═O). The reaction mixture was poured in water (1.5 L) and extracted with ethyl acetate (AcOEt) (3×1.5 L). Gathered organic phases were dried over magnesium sulfate (MgSO4), filtered and concentrated under reduced pressure. The residue was taken up into diisopropylether (1.5 L) and the solid formed (Ph3P═O) was filtered. The solvent was concentrated under reduced pressure and the residue purified by column chromatography eluting with a mixture of heptane with AcOEt (90/10; v/v) to give 145 g (100%) of tert-butyl (3S)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxy]pyrrolidine-1-carboxylate (c) as a colorless oil. 1H NMR (400 MHz, DMSO-d6, δ ppm): 1.27 (s, 12H); 1.39 (s, 9H); 2.05 (m, 1H); 2.14 (m, 1H); 3.37 (3H); 3.55 (m, 1H); 5.05 (s, 1H); 6.94 (d, J=8.4 Hz, 2H); 7.61 (d, J=8.4 Hz, 2H) |
100% | With diamide; triphenylphosphine; In tetrahydrofuran; at 20℃; for 24h;Inert atmosphere; | To a solution of 4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenol (82.7 g, 364.51 mmol) in THF (2 L) was added under argon (R)-1 -N-Boc-3-hydroxypyrrolidine (84.43 g, 437.41 mmol) followed by Ν,Ν,Ν',Ν'-tetramethylazodicarboxamide (99.1 g, 546.77 mmol). The clear reaction mixture turned orange and triphenylphosphine (143.41 g, 546.77 mmol) was added. The reaction mixture was stirred at room temperature for 24 hours, meanwhile a precipitate of triphenylphosphine oxide formed (Ph3P=0). The reaction mixture was poured in water (1 .5 L) and extracted with EtOAc (3x1 .5 L). Gathered organic phases were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was taken up into diisopropyl ether (1 .5 L) and the solid formed (Ph3P=0) was filtered. The solvent was concentrated under reduced pressure and the residue purified by column chromatography eluting with a mixture of heptane and EtOAc (90/10; v/v) to give 145 g (100%) of tert-butyl (3S)-3-[4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)phenoxy]pyrrolidine-1 -carboxylate (c) as a colorless oil. LC/MS (m/z, MH+): 390 |
100% | With diamide; triphenylphosphine; In tetrahydrofuran; at 20℃; for 24h;Inert atmosphere; | To a solution of 4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenol (a) (82.7 g, 364.51 mmol) in THF (2 L) was added under argon (R)-1 -N-Boc-3-hydroxypyrrolidine (b) (84.43 g, 437.41 mmol) followed by N,N,N',N'-tetramethylazodicarboxamide (99.1 g, 546.77 mmol). The clear reaction mixture turned orange and triphenylphosphine (143.41 g, 546.77 mmol) was added. The reaction mixture was stirred at room temperature for 24 hours, meanwhile a precipitate of triphenylphosphine oxide formed (Phi3P=0). The reaction mixture was poured in water (1 .5 L) and extracted with ethyl acetate (AcOEt) (3x1 .5 L). Gathered organic phases were dried over magnesium sulfate (MgS04), filtered and concentrated under reduced pressure. The residue was taken up into diisopropylether (1 .5 L) and the solid formed (Pfi3P=0) was filtered. The solvent was concentrated under reduced pressure and the residue purified by column chromatography eluting with a mixture of heptane with AcOEt (90/10; v/v) to give 145 g (100%) of tert-butyl (3S)-3-[4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)phenoxy]pyrrolidine-1 -carboxylate (c) as a colorless oil. (0121) 1H NMR (400 MHz, DMSO-d6, d ppm): 1 .27 (s, 12H); 1.39 (s, 9H); 2.05 (m, 1 H); 2.14 (m, 1 H); 3.37 (3H); 3,55 (m, 1 H); 5.05 (s, 1 H); 6.94 (d, J = 8.4 Hz, 2H); 7.61 (d, J = 8.4 Hz, 2H). |
1.76 g | With triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; at 0 - 20℃; | In Step 1, Compound 54 (1g) was reacted with Compound 55 using PPh3 and DEAD in THF. The reaction was cooled to 0 C and allowed to warm to room temperature while stirring overnight. Following purification, Compound 56 (1.76 g) was obtained. In Step 2, Compound 56 (1.7 g) was subjected to deprotection conditions using TFA in DCM. The reaction stirred for 2 hours at room temperature and was purified to afford Compound 57 (1.25 g). In Step 3, Compound 57 (200 mg, 1 eq.) was dissolved in DMF and reacted with 1-fluoro-3-iodopropane (1.2 eq.) in the presence of K2CO3 (3 eq.). The reaction was heated to 110 C and allowed to stir overnight. Purification afforded Compound 58 (70 mg). Compound 58 (70 mg, 1 eq.) was then coupled to Compound 59 using Pd(PPh3)4 and K2CO3 in dioxane. The reaction was heated to 110 C and allowed to stir overnight. Following purification, 95 mg of Compound 60 was obtained. The 1HNMR was indicative of product. In Step 5, Compound 60 was subjected to hydrogenolysis. Compound 60 (90 mg) was dissolved in CH3COOH and MeOH and Ph(OH)2 was added. Following hydrogenolysis at 60 C for 2 hours and purification, Compound 108 (14.8 mg) was obtained.1HNMR, LC-MS, and HPLC were indicative of Compound 108. |
Tags: 4-Hydroxyphenylboronic acid pinacol ester | Organoboron | Aryls | Pinacol Boronates | Organometallic Reagents | Organic Building Blocks | Boronic Acids/Esters | 269409-70-3
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P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position 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. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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