484 Communications ‘A Low Hazard Procedure for the Laboratory Prepara- tion of Polynitrate Esters Cruig D. Mangia, Clifrd E. Keistorttason, Mitchel M. Rorawo, Anthony P, Maxrana, Michael W. Baas Thiokol Corporation, Bisham City, Utah $4302, USA. ‘We would lke to report a convenient, low hazard procedure for the laboratory preparation of nitrate esters of polyols, This method provides product in high yield and of analytical purity without resorting to physical methods of purification, ‘This procedure has been utilized to prepare from 24 g up. 10.450 g of nitrate ester. Our method involves the nitration of the polyol with mixed nitric-sulfuri acid in the presence ‘of dichloromethane. The reuction conditions are monitored by an Ingold Type 488 redox potential probe! Dichloromethane solvent is present in these reactions pri marily to redice the safely hazards associated with the pre- paration and the products. This is done in three ways (a) the solvent deercases the impact sensitivity of the nitrate ester: (b) it removes the nitrate ester from the aitration medium so that side reactions are minimized: and (c) it serves a a heat sink in case of too rapid heat eneration. NOs 1 HaS0g 1 aCla HO=(CHg)—0H | Ee (pN—0~(cHH2};-O-NOz The Ingold redox probe is present in the nitrating acid to monitor the nitrite ion formation, which could generate unstable nitrite esters. The theoretical aspects of the wiliza tion of these probes in the nitroglycerine manofacturing process have been described by Ohman?, The nitrite anion can be minimized by starting with pure polyol and can be kept at a reduced level by using the probe to control the addition rate of the polyol. The polyol is added to the nitrating acd at rate which keeps the potential nearly “Table, Nitration of Polyols syntuesis constant, In a typical addition, the initial probe reading will be near —001 volt und when the addition is complete ial should be near 0.07 volt, with a temperature If the potential nears —0.20 volt the reaction ‘may be Out of control and at ~0.35 volt it may undergo rapid and violent decomposition’, ‘An additional procedure required 1 reduce the nitrite anion concentration involves the careful preparation ofthe aitrat- ing acd solution. Ths is easily achieved by the stow addition oesly prepared anhydrous iti acid (oan equal volume of cooled fuming sulfuric acid while maintaining 2 constant temperature. Te trite concentration of this nitrating acid is determined by a permanganate titration technique’. The initial value should be near 0.016%, as nitrous acid and this material should no longer be used for nitration afer the nitrous acid concentration reaches 005% With the use of these techniques on a laboratory scale, several polynitrate esters could be easily prepared (see Table) with the minimum of hazard and in high yield and purity The additional advantages of this method, as previously ‘mentioned, include desensitization ofthe product by diluting in the solvent, maintaining stable reaction conditions with the redox probe, and the avoidance of unstable side products sul as nitrite esters, CAUTION: These nitrate esters should be prepared behind safety shields in an isolated luboraory, since the prot tare highly explosive materials. Asa further safety precaution or minimize transfer of hazardous materials and to mainain temperature control, we recommend the use of a jackeel, three-neck flask witha bottam discharge, Teflon stopeoek. All ‘asst glass joints shouldbe Teflon cape wrapped. All washings should be done in the reaction flask. Experience with these rections should be gained on «small scale before attempting them on a larger scale. The following procedure is typical Payot Yar mp tmp Reng Li Relate Mer ras races fetta vo-oneke-on-on tans uns Gatnioy om wo-cny-biedn=ct-oh By ae CottaNOn on ©), ae im vo-temn-ou “ ans aaa GMO wa +The 18. spocra of the product nitrate eters ae identical (0 those of authentic samples. Ref §. page 3 «All products gave satisfactory nitrogen analyses (N +0.07%): values were determined on samples as isolated by removing reaction solvent under redo pressure Ret. §, page 166 fr cabttienions, considerable material was discarded since she mannitol hexanirate was insoluble in the dichloromethane © Mannitol hesuniteate was rccrystilzed from ethanol before determination of nitrogen analysis. Ref 5, page 168July 1977 ‘Communications 485 Preparation of1-Propanedil Dinitrate: The nitrating acid is prepared by slowly adding freshly prepared anhydrous nitric acid (200 ml, 486 mol) (0 funing sulfuric acid 1200 mi) while siring and maintaining temperature of less than IS", After the addition of distilled dichloromethane (1,500, mi) the mixture iseooled to 12° andthe initial potential reading ‘ofthe Ingold Type 488 redox probe is 1006 volt The 1 3-propane- iol (760 1.00 mol) is slowly added to the stirred nitraing mixture at a rate which wil keep the potential as steady as possible with temperatuc lessthan 12". Aer the (3-propanediol ‘klition i completed, the redox potential is ~204S volt at 10°. The seat acid is immediately removed through the bottom di charge stopcock and the dichloromethane phase i washed in ‘the reaction isk with water ($00 ml 1), 10% aqueous sodium Ccbonate solution (400 mi» 3}, 10% ayueous urea solution (500 mlx Ih and water (500 mlx 3), Thi organie phase is driod over anhydrous sodium sulfate followed by 4A molecular sieves. The ‘olsen i removed under reduced pressure to give the L3-propane- iol dinitrate: yok: 1480 186") CHaNsO, cle. N 1686 (166.1) found 1679 [LR neat an =2990, 2905, 1640, 1288 om We gravelly acknowledge Mr. Paul Mosher and the late Mr Witham 0. Brimyjoin ofthe Naval Oninance Station, Indian Heal ‘Marsan for their helpfi discssionsohich le 10 the wse of the Ingold reo probes Recived: October 25, 1976 (Revised form: January 28, 1977) "These redox probes Now Jersy * V, Ohman, Sven. Kem. Tidsr. 78 20 (1966) and references ted thercin, To our knowledge utilization of these. probes fon a laboratory scale and with polyols other than slyeerine and diethylene glycol has not been reported » P. Mosherand W.O. Brimijoin, Naval Ordnance Station, Indian Head, Maryland: personal communication. “1M, Kolo, EB. Sandel. EJ. Meshan, . Brokenstein, Quanciative Chemical Analysis, Ath Edit, The Macmillan Com: Pung 1969p. 8M, * T.Urbatshi Chemis and Technolog of Exposces, Pergamon Press, Oxford 1968 ailable rom Chemapec, In. Hoboken,