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The Late Show with Rob! Tonight's Special Guest: Hydrazine The Late Show with Rob! Tonight’s Special Guest: Hydrazine Robert Matunas December 8th, 2004 Last One of the Year!! Schmidt, E. W., Hydrazine and Its Derivatives, Wiley-Interscience, New York, 2nd edn., 2001 Ragnarsson, U. Synthetic methodology for alkyl substituted hydrazines, Chem. Soc. Rev., 2001, 30, 205-213 The Late Show with Rob! Tonight’s Special Guest: Hydrazine Robert Matunas January 5th, 2005 Happy New Year!!! Schmidt, E. W., Hydrazine and Its Derivatives, Wiley-Interscience, New York, 2nd edn., 2001 Ragnarsson, U. Synthetic methodology for alkyl substituted hydrazines, Chem. Soc. Rev., 2001, 30, 205-213 The Late Show with Rob! Tonight’s Special Guest: Hydrazine Robert Matunas January 12th, 2005 (Third Time’s the Charm!) Schmidt, E. W., Hydrazine and Its Derivatives, Wiley-Interscience, New York, 2nd edn., 2001 Ragnarsson, U. Synthetic methodology for alkyl substituted hydrazines, Chem. Soc. Rev., 2001, 30, 205-213 The Late Show with Rob! Tonight’s Special Guest: Hydrazine Robert Matunas January 19th, 2005 (I’ve Forgotten Everything) Schmidt, E. W., Hydrazine and Its Derivatives, Wiley-Interscience, New York, 2nd edn., 2001 Ragnarsson, U. Synthetic methodology for alkyl substituted hydrazines, Chem. Soc. Rev., 2001, 30, 205-213 Overview • Historical development of hydrazine (and friends) • Industrial outlook on hydrazine compounds • Selected synthetic methods for preparing simple alkyl hydrazines • Some Myers Hydrazine Chemistry It All Started with H. Emil Fischer (1852-1919)… N NH2 N HNO2 H Sulfite salts N NH2 Phenylhydrazine! Phenylhydrazine was the first hydrazine compound discovered; Fischer synthesized it serendipitously in 1875 by reduction of the corresponding diazonium salt. Fischer, E. Ber. Dtsch. Chem. Ges., 1875, 8, 589. Some “Sweet” Synthesis Fischer had been working on sugar syntheses, but lacked methods for obtaining the pure compounds. Imagine making a sugar from scratch and then failing to isolate it! Phenylhydrazine to the rescue! CHO HC NNHPh HC NNHPh CHOH PhNHNH2 CHOH PhNHNH2 C O (CHOH)3 AcOH (CHOH)3 AcOH (CHOH)3 CH2OH CH2OH CH2OH Sugar HC NNHPh PhNHNH2 C NNHPh AcOH (CHOH)3 CH2OH Osazone Fischer, E. J. Am. Chem. Soc., 1890, 12, 340-8. Fischer, E. Ber. Dtsch. Chem. Ges., 1884, 17, 579. Some Other Early Fischer Syntheses… Fischer used some of the following strategies to prepare ~20 different hydrazines, all before free hydrazine itself was known. R R R 1 nitrosation 1 reduction 1 NH N NO N NH2 R2 R2 R2 O O O R hydrolysis R R nitrosation R R reduction R R HN NH N N N N N N 2 H H H H NO NH2 Ph Bz Ph Bz Ph H Ph benzoylation methylation debenzoylation NN NN HN NH2 NNH Bz Bz CH3 H CH3 The last preparation of a 1,2-disubstituted hydrazine anticipates the modern dependence on protecting groups in synthesis. Ragnarsson, U. Chem. Soc. Rev., 2001, 30, 205-213. …but Preparing Free Hydrazine Itself Took Time Curtius eventually prepared free hydrazine (as the hydrate) via a circuitous route. The year was 1887, already 12 years after the discovery of phenylhydrazine. Since that time, about 20 other hydrazine derivatives were already known! O HN NH + HN NH H KOH H 2 EtO KO2C CO2K HO2C CO2H N NN NN N O H+ HO 2 H2NNH2 + 2 OH O Hydrazine! Curtius, J. Prakt. Chem. 1889, 39, 107-39. Molecular Properties of Hydrazine Of the possible conformations for hydrazine, the gauche form is favored. H H 112° H NN 1.45 Å 1.02 Å H Bond Strengths: Rotational Barrier: N-N: ~ 50-60 kcal/mol 6-10 kcal/mol N-H: ~ 80-90 kcal/mol (vs. ~ 3 kcal/mol for ethane) Hydrazine Production Today Of the many methods available, the Raschig process is still in use (discovered 1907): NH3 +NaOCl ClNH2 +NaOH ClNH2 + NH3 + NaOH H2NNH2 + NaCl + H2O Optimal ratio of reactants is 33:1 NH3:NaOCl! The only waste produced is brine, but this is still a significant issue on plant scale. H2NNH2 + ClNH2 2NH4Cl + N2 The major side reaction is destruction of the product hydrazine by further reaction with chloramine. An Improved Process for Hydrazine Production: The Atofina-PCUK “Cycle” R3 R1 R1 R O R1 3 O O + NH3 NH NH + R3OR3 - H2O R2 R2 R2 O + NH3 - H2O R1 O + 2 H O R1 R1 2 R1 N N R2 N R2 R2 - H O 2 R2 NH2 R1, R2 = Me or Et; R3 = H H2NNH2 ! Raschig Process: 4 tons NaCl/ton of hydrazine; 60% yield (based on NH3); 125 kWh/ton hydrazine required Atofina-PCUK: No byproducts; >80% yield (based on NH3); 16 kWh/ton hydrazine required Hydrazine in the Wonderful World Around Us • Free hydrazine on the Earth is not known (because of air oxidation), but was assumed to be present in the primordial environment. • One major application of hydrazine today is as a rocket fuel (along with methylhydrazine as well). First developed by Germany for powering prototype jet engines in the Messerschmitt ME163 (WWII), simple hydrazines are still in use today by NASA for specific applications requiring certain types of thrust. For example, the International Space Station uses dimethylhydrazine for propulsion to maintain orbit and control attitude. • Aside from pesticides and pharmaceuticals, the other major hydrazine application is in the deoxygenation of boiler feed water. This decomposition is catalyzed by metals such as copper and cobalt, and most likely also by metallic species leached gradually from pipe systems (especially nickel). H2NNH2 +O2 N2 +2H2O Naturally Occurring Hydrazines OH H O N Me N N N H H H O HO Agaritine, from the N.A. commercial Gyromitrin, from the false morel NH2 mushroom, Agaricus bisporus, 777 mushroom, Gyromitra esculenta O million lbs. grown in 1996 CH H N 3 NH2 N OH H2N N HN OH OH NH O CH O 2 3 O O Negamycin, antibiotic from Linatine, found in linsead Streptomyces purpeofuscus meal and flax Some Synthetic Hydrazines with Useful Properties NHNH O 2 O H N N NHNH N 2 H N N N Isoniazid (TB) Iproniazid (early antidepressant, Hydralazine but toxic) (antihypertensive) F3C O N N N N NH O N SMe NH NH2 O SO2NH2 Sencor Maleic hydrazide Celebrex (Herbicide) (plant growth retardant) (NSAID) Maleic hydrazide is marketed under the amusing trade names Slo-Gro, Royal Slow-Gro, Slows-It, De-Sprout, De-Cut, Fair Plus, Sprout Stop, and Super Sucker-Stuff The Woes of Hydrazine Alkylation Direct alkylation of hydrazine is problematic for the same reason that direct alkylation of primary amines is problematic: overalkylation is competitive with monoalkylation. R NH RX NH R NH 2 2 ++2 - Whoa! H2N Base HN N R NNH2 X R R R CD3 CD3I NH2 NH2 D3C NH2 + NH H2N Base HN + N HN CD3 CD3 CD3 56.1% 42.4% 1.5% Anthoni, U.; Larsen, C.; Nielsen, P.H. Acta Chem. Scand., 1968, 22, 1025-1035. Direct Alkylation Can Sometimes Be Feasible… Direct alkylation can occasionally be feasible if (1) the electrophile is very bulky; (2) the electrophile contains an EWG; or (3) an activated alkene is used. (1) NH2 Ph3CCl Ph3C NH2 H2N N H O O X R (2) NH2 NH2 H2N R N H EWG H NH R N 2 H2N EWG (3) H2N R Some Strategies for Monsubstituted Hydrazines These procedures are invariably reliant on protecting groups of one form or another. An important limitation is that only activated primary electrophiles are viable in these reactions. Ph OP H Ph2OP RBr/PTC 2 HCl NNH NNH HN NH2 NaOH 2 2 R R Boc Boc H Bu4NHSO4, KOH 2N HCl (2 eq.) HN N NN NNH2 RBr, PhCH , 80 oC THF, reflux, 3h 3 R R O O Boc Boc Boc H Ph P, DEAD MeNHNH2 TFA N NH 3 N N H NN H2NN ROH 2 R R R O O Ragnarsson, U. Chem. Soc. Rev., 2001, 30, 205-213. Meyer, K. G. Synlett, 2004, 13, 2355-2356. More on Monosubstitution Reductions of hydrazones and hydrazides also leads to monosubstituted hydrazines, including ones with secondary alkyl groups. O H LAH/AlCl H 3 NNH NNH2 2 R R R1 R1 R1 H H2NNH2 H2/cat. or O N NH2 N NH2 NaCNBH3, etc. R2 R2 R2 Ragnarsson, U. Chem. Soc. Rev., 2001, 30, 205-213. 1,1-Disbustituted Hydrazines R R1 R X 1 2 NNH HN NH2 2 R2 R R1 R1 R1 1 1) Nitrosation H2N-X NNH NH NNH NH 2) Reduction 2 2 R R R2 R2 2 2 X = -Cl, -OSO3H R1 O R1 P R1 R Deprotection NH+ N NNH NNH2 R2 P R2 R2 More on that oxaziridine later… Ragnarsson, U. Chem. Soc. Rev., 2001, 30, 205-213. 1,2-Disubstituted Hydrazines A bit more troublesome than the 1,1-disubstituted case: Ph2OP Ph2OP Ph2OP Ac R1Br/PTC AcCl NNH2 NNH2 NN H R1 R1 H Ph OP Ac H R R Br/PTC 2 2 2 NN HCl NN R1 R2 R1 H Ragnarsson, U. Chem. Soc. Rev., 2001, 30, 205-213. “Higher” Hydrazines? No pain, no gain! H H H Ts H Ts PhH C Ts TsCl, pyr, Boc O, DMAP, BnBr, K CO , TBAHS, 2 NN NN 2 NN 2 3 NN 98% MeCN, 99% MeCN, 3 d, quant. Cbz H Cbz H Cbz Boc Cbz Boc PhH C H PhH C CH 2 MeI, K CO -NaOH, 2 3 1) TFA, DCM, 93-99% Mg, MeOH, NN 2 3 NN sonication, 98% TBAHS, PhH, quant. 2) p-FC6H4COCl, pyr., 99% Cbz Boc Cbz Boc PhH C CH PhH2C CH3 2 3 1) TFA (reflux) NN NN 2) p-FC6H4SO2Cl, 72% p-FC H SO p-FC H Cbz p-FC6H4 6 4 2 6 4 O O Grehn, L.; Lönn, H.; Ragnarsson, U.
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