Document rxLZ6XMzYEmJyO5ZQVnkey2er

UN1RDYAL UNIROYAL CHEMICAL Division of UNIROYAL, Inc. Elm Street Naugatuck, Connecticut 06770 203-723-3278 August 23, 1979 Ms. Mary Donao PPG Industries P. O. Box 1000 Lake Charles, LA 70602 Dear Mary: In response to your recent inquiry, I have enclosed our product bulletin and safety data sheet for Cyclohexene Oxide. With regard to the storage stability of this product, we are continuing testing on material that is undergoing ambient aging. Based upon, results we have observed to date, Naugard CHO should be stable (i.e. meet your purchase specifications) under ambient aging for at least six months. I believe that similar studies are being conducted at Barberton under the supervision of Dr. Don., Reich and suggest that you contact him for further information. If there is anything further that I can do to help you, please don't hesitate to call me. Very truly yours UNIROYAL CHEMICAL Gea Group Leader Specialty Chemicals GJH:ml1 Enc. UNIROYAL CHEMICAL Division of UNIROYAL, Inc. Naugatuck. Connecticut 06770 Naugatuck6 Chemicals CcHioO CYCLOHEXENE OXIDE CHi CHx CH* TYPICAL PROPERTIES Appearance: colorless liquid Purity: 98% Boiling Point: ^6F, (130 C.) :. , : Specific Gravity @ 25/25 C. Density @ 60 8.1 lbs./gal. (970.4 Kgs/in 3) Flash Point (TOC): 80.6 F. (27 C.) Refractive Index @ 30 C. - 1.450 Alkyl and aryl mercaptans react with cyclohexene oxide in an analogous manner (11). 0.+ CH3CH2CH2SH --SCH2CH2CH3 --OH SHIPPING AND CONTAINERS Steel Drum........................................ 425 pounds net CYCLOHEXENE OXIDE, CHEMICAL REACTIONS Ammonia and amines open the oxide ring with the formation of a~ amino alcohols. Thus, aqueous or alcoholic ammonia reacts with cyclohexene oxide to give 2-aminocycIohexano! when the ammonia is in excess or bis (2-hydroxycyclohexyl) amine when the oxide is in excess (2, 5, 6, 7). Cyclohexene oxide, also known as 1,2-epoxycyclohexane and 7-oxabicyclo (4.1.0) heptane, is a highly reactive compound, which resembles ethylene oxide in most of its reactions. In general, its reactions involve cleavage of the oxide ring (5, 7). Water readily opens the oxide ring of cyclohexene oxide with the formation of ci$-l,2-cyclohexanediol (2,5,6,7). O>o+,bo--' O^H Alcohols, phenols, and naphthols also bring about cleavage of the oxide ring of cyclohexene oxide. For example, cyclohexene oxide reacts with methanol at 150C. to give 2-methoxcyclohexanol (3, 7, 9). o*.~---O^* Similarly, treatment of cyclohexene oxide with alcoholic ethylamine gives 2-ethylaminocyclohexanol (6). H CH3CH2NH2 --NCH2CH3 O-OH SL 049710 UMROYAL Organi: acids and acid anhydrides also bring about cleavage of the oxide ring. For example, treatment of cyclohexane oxide with benz ic acid yields 1,2-cyclohexanediol monobenzoate (3), while treatment with p*toluenesulfonic acid yields 1,2-cyclohexanediol mono-p-toluencsulfonate (7). Sodiomalonic ester and similar substances, such as acetoacctic ester and cyanoacctic ester, open the oxide ring. Thus, treatment of cyclohexene oxide with sodio malonic ester followed by hydrolysis and decarboxyla tion results in formation of the y-lactone of 2-hydroxycyclohexaneacetic acid (7, 13). Hydrogen halides and other inorganic halides (e.g. potassium bromide, ammonium chloride, zinc chloride) combine with cyclohexene oxide to form halohydrins (I, 2.7.14). . _ .. 1: i i . Treatment of cyclohexene oxide with aldehydes or ketones in the presence of an acidic catalyst such as stannic chloride or boron trifluoride produces cyclic acetals or ketals. For example, reaction with 2-butanone yields the ketal, 2-methyl-2-ethylhexahydro-l,3-benzodioxole (7). O (S' :q.4 OHiCCHeCHa i + KOH r^]->c/cH- V/*-- ' CH-CHj Alkyl and acyl halides also open the oxide ring (2). o + CHaCHal o + CHsCOBr --OOCCHs O-Br Dialkylmagnesium and aryllithium in ether solution react with cyclohexene oxide to produce 2-alkyl- or 2-arylcyclohexanol, respectively (7). Mg(CsH;)s ao---------------- . LiCcH; ao -- --CH;. 0--OH Reduction of cyclohexene oxide to cyclohexanol can be effected by reducing agents (e.g. lithium aluminum hydride in ethyl ether) or by catalytic hydrogenation over reduced nickel (5, 6, 7, 15). Dehydration of cyclohexene oxide to 1,3-cycIohexadiene can be accomplished by the action of thoria or phthalic anhydride (4), O SL 049711 --COOH ---POOH An important reaction of cyciohexene oxide is the reaction with Grignard reagents, which, in some cases, results simply in the formation of the expected 2-alkyl- or 2-arylcycIohexanol. For example, 2-benzylcyclohexanol is obtained by treatment of cyciohexene oxide with benzylmagnesium chloride (7. 8). Heating cyciohexene oxide at 630-780 C. result;, in its rearrangement to cyclohexanone (12), while treatment of cyciohexene oxide with propyllithium results in its rearrangement to 2-cycIohexcnol (10). C.;H.-.CHjMgC 1 --CHsCaHa a 0----------------------------- ' -OH However, the reaction of a Grignard reagent with cycio hexene oxide more often leads to ring contraction. Thus, cyclopentyl p-phenylethylcarbinol is obtained by reaction of cyciohexene oxide with i-phenylethylmagnesium bromide (7, 8). OH GiH.-.CH-CHsMgBr ------------------ --CCHaCHaCiiHs I H . . Apparently* this rearrangement is brought about by ^ ,r '~_reactiooofcyclohexehe oxide with MgX2(from 2RMgX r. . ~;--'..^R2Mg/ +. MgX2) to foffn 'the ^lohydrin which is converted: to the'smaller ring when heated strongly. Similarly, cyclopentylformaldehyde is formed when cyciohexene oxide is heated with magnesium bromide in dry ether (7, 8). Rearrangement to cyclopentylformaldehyde also occurs when cyciohexene oxide undergoes the Reformatsky reaction (7). APPLICATIONS Many possible uses are envisioned for cyciohexene oxide in the drug and specialty fields because of its broad range of reactions and unique structure. It's epoxide structure is especially useful in applications where an HQ scavenger is c ii::cc i; CTI -* STORAGE AND HANDLING Cyciohexene oxide is supplied in non-returnable steel drums. It is a flammable, highly reactive compound. Inhalation of vapors or contact with skin or mucous membrane should be avoided. B rC H -COOCvH Zn OH --CCH.COOC.H-. I H TOXICOLOGY BACKGROUND Cyciohexene oxide has an acute oral LD50 f r rats of 1.09 mis/ Kg. Acute dermal LDso for rabbits is 0.63 mis/ Kg. Inhalation exposure of rats has an estimated LC50 26^0 ppm. Eye exposure of rabbits to undiluted cyciohexene is moderately severe. 1. Bartless, J. Am. Chem. Soc. 57, 224 (1935). 2. Bedos, Compt. rend. 185, 562 (1926). 3. Bedos, Compt. rend. 183, 750 (1926). 4. Bedos and Ruyer, Compt. rend. 188. 962 (1929), 5. Brunei, Compt. rend. 137, 62. 198 (1903). 6. Brunei, Ann. chim. ct phys. 6, 200 (1905). 7. Elderfleld, Heterocyclic Compounds, John Wiley & Sons, lne.. New York, vol. 1, pp. 22-31, 41-42, 55-58. 8. Gilman ct al. Organic Chemistry--An Advanced Trea tise, John Wiley & Sons, Inc., New York, 1943, vol. I, pp. 512-514. 9. Guss, Rosenthal, and Brown, J. Org. Chem. 20, 909 (1955). 10. Letsinger, Traynham. and Bobko, J. Am. Chem. Soc. 74, 399 (1952). I I.Nenit/escu and Scarlatescu. Chem. Ber. 68B. 587 (1935). !2.Riceand Stallbaumcr. J. Am. Them. Soc. 64. 1527 (1942). l3.Rodd. Chemistry of Carbon Compounds. Elsevier Pub lishing Co.. New York. 1953. vol. II pt. A, p. 321. !4.Sen and Barat, Quart. J. Indian Chem. Soc. 4. 22 (1927). 15.Trevoy and Brown. J. Am. Chem. Soc. 71, 1675 (1949). SL 049712 I. UHIRDYAL r-v- UKIROYAL CHEMICAL Division of UNIROYAL, Inc. Elm Street Naugatuck, Connecticut 06770 (203) 723-3000 PRODUCT SAFETY DATA SHEET Trade Name: Uses: Chemical Name: CHO Chemical Intermediate Cyclohexene oxide Chemical and Physical Properties Appearance: Colorless liquid - pungent odor : Boiling Point: 130C. Solubility;_ . Soluble in alcohol, insoluble in water Specific Gravity: 0.967 at 25 C. Corrosivity: Not corrosive Volatility: Highly volatile Fire and Explosion Hazard Flash Point: "81F. (27C.) - TOC Autoignition Temperature: 705F ---------- Flammable Limits (Vol. %) Upper: 12.36 Lower: 1.15 . Special Decomposition/Reactivity Precautions: Highly reactive compound. Reactions usually involve cleavage of oxide ring. Fire Fighting Media and Procedures: C02 dry chemical, foam m SL 049713 PRODUCT SAFETY DATA SHEET (cont.) CHO Health Related Data Specific Hazard: Inhalation of vapor. Handling Precautions: Use only in well ventilated areas. Avoid skin and eye contact. First Aid Procedures: If eye contact occurs, flush with water and get medical attention. If skin contact occurs, wash immediately with soap and water. Toxicology Background: Acute Oral LD5Q(rats): 1.09 mls/Kg Acute Dermal LD50(rabbits): 0.63 mls/Kg ^Inhalation Exposure (rats): ^ ~ ' A) 'Inhalation at 13,000 ppm * 1 hour: 6/6 killed 1/2 hour: 0/6 killed B) Exposure' over 4 hours (rats): 4.000 ppm: 6/6 killed 2.000 ppm: 1/6 killed * *' * C) Estimated LC50 - 2650 ppm Eye Exposure (rabbits): A) Undiluted: Moderately severe B) .15% solution in propylene glycol caused corneal necrosis. C) 57o solution in propylene glycol caused traces of corneal necrosis. Storage and Waste Disposal Storage: Store in a cool place. Product is flammable. Avoid exposure to heat and ignition source. Clean-up: Spills may be absorbed on inert carrier. Disposal: Incineration is best method of disposal if allowed by environmental rules. Data Supplied By: cT 04971* R. J. Dowling Product Saf ty Specialist