Studies of nucleophilic attack on tris (pentafluorophenyl) phosphine and its oxides

The reaction of tris(pentafluorophenyl)phosphine [5] with the nucleophiles dimethyl formamide (DMF), hexamethylphosphoric triamide (HMPA), diethyl formamide (DEF), hexaethylphosphoric triamide (HEPA), hydrazine, N,N-dimethyl hydrazine (in presence and/or absence of KF), phenylhydrazine, ammonium hydroxide, formamide, aniline, sodium hydrogen sulfide, and hexaethylphosphorous triamide was investigated. The reaction of [5] with DMF and HMPA gave the same product, namely tris-[4-(N,N-dimethylamino)-2,3,5,6-tetrafluorophenyl]phosphine [12] but in higher yield in the case of HMPA. Compound (5] also reacted with DEF to give tris[4-(N,N-diethylamino)-2,3,5,6-tetrafluorophenyl] phosphine [14]. When [51 was treated with HEPA, it gave a mixture of bis(pentafluorophe~yl)-(N,N-diethylamino-tetrafluorophenyl)phosphine, pentafluorophenyl-bis-(N,N-diethylamino-tetrafluorophenyl)phosphine and tris (N,N-diethylamino-tetrafluorophenyl)phosphine. Treatment of [5] with aqueeus hydrazine solution in excess ethanol gave tris(4-hydrazo-2,3,4,6-tetrafluorophenyl)phosphine [1s1 in high yield while reaction with aqueous hydrazine led to C-P cleavage and production of tetrafluorophenyl hydrazine. With N,N-dimethyl hydrazine, [5] gave tris(4-N,N-dimethylhydrazine-2,3,5,6-tetrafluorophenyl) phosphine {20j. The latter could be obtained in higher yield and shorter reaction time, by the addition of KF. The reaction of compound {51 with phenylhydrazine in THF gave bis(pentafluorophe~yl)-4-S-phenylhydrazino- 2,3,5,6-tetrafluorophenyl phosphine [22] in low yield. Reaction of [5] with ammonium hydroxide in THF at high pressure in the presence of KF gave tris-~4-amino-2,3,5,6-tetrafluorophenyl)phosphine [25]. Similarly, formamide led to a mixture of (C6F4NHZ)3P, (C6F4NHZ)ZPC6FS, (C6F4NHZ)ZPC6F4NHCHO, and C6F4NHZP(C6Fs)(C6F4NHCHO). When [5] was treated with aniline, a mixture of mono-, di-, and tri-substituted products was obtained. Sodium hydrogen sulfide in ethylene glycol/ pyridine led to C-P cleavage and the isolation of pentafluorobenzene and tetrafluorothiophenol. Reaction of [5] and its oxide [35] with different alkoxides in the corresponding alcohols led mainly to C-P bond cleavage products, with the exception of one case where sodium methoxide was used in ether, and which led to tris-(4-methoxy-2,3,9,6-tetrafluorophenyl)phosphine [37]. On the basis of various spectroscopic data, it was concluded that the para position in compound [5] was generally the favoured site of attack.

District general orders of Maj.-Gen. Sir Isaac Brock from June 27th, 1812-Oct. 16th, 1812 [and] instructions sent to officers commanding forts / by Maj.-Gen. Brock shortly before the attack on Queenston. --

"Certain of these orders ... have been printed in Col. E. Cruikshank's Documentary history of Niagara." Created on behalf of the Women's Canadian Historical Society of Toronto

Letter from the Secretary of State to Mr. Monroe, on the subject of the attack on the Chesapeake : the correspondence of Mr. Monroe with the British Government ; and also Mr. Madison's correspondence with Mr. Rose on the same subject. --

March 23, 1808. Printed by order of the House of Representatives.

Letter from the Secretary of State to Mr. Monroe, on the subject of the attack on the Chesapeake : the correspondence of Mr. Monroe with the British Government; and also Mr. Madison's correspondence with Mr. Rose on the same subject

March 23, 1808. Printed by order of the House of Representatives.

Thoughts upon the conduct of our administration in relation both to Great Britain and France, more especially in reference to the late negotiation, concerning the attack on the Chesapeake

Printed at the Repertory Office

Naval and military chronicle of the United States : attack on Fort Erie

Includes rare 1816 battle plan map.

Independent Chronicle Vol. XLVI No. 3477- August 8, 1814

A semi-weekly paper that was published from 1801 to 1817. It was previously called the Independent chronicle and the universal advertiser, and was later the Independent chronicle and Boston patriot (Semiweekly). Publishers were Abijah Adams and Ebenezer Rhoades. Topics of interest in this issue include: Page 1: notice from the U.S. War Department seeking proposals for the supply of rations to troops; account of the battle of Bridgewater; list of important military figures wounded in the battle; news of prisoner exchange; Americans and the British negotiate and new prisoner exchange convention; Page 2: report of more British troops sailing to North America; report of some Indian tribes signing a treaty to fight against the British; report of battle near Detroit; report of militia moving from Fredricksburg, Virginia to Baltimore, Maryland; report of troop numbers and casualties in the battle of Bridgewater; report that Commodore Chauncey has recovered from his illness; news of American Naval forces sailing from Sackett's Harbor; Indian tribes sign peace treaty with U.S.; news of U.S. relations with Indians in the southern U.S.; account of battle of Bridgewater and list of casualties; report of the number of men killed and wounded on both sides in the battle of Chippewa; Page 3: report of surprise attack on the British; news of warship movements in and out of Halifax; frigate Java launched in Baltimore; news of British ship movements; 3 companies of Massachusetts militia arrive at Fort Warren; news of ship movements in and out of the Port of Boston; various Marshal's notices alleging U.S. ships supplying goods to the British;

Letter written by Mahlon Taylor to Samuel Clarke commenting on US troops during Fort George occupation, July 26, 1813

Fort George, situated on the west side of the Niagara River in Niagara-on-the-Lake, served as the headquarters for the Centre Division of the British Army during the War of 1812. On May 25, 1813, the Americans launched an artillery attack on the Fort, destroying most of the buildings. Two days later, the Americans invaded the Town of Niagara and occupied Fort George. They remained in the Fort for almost seven months, but suffered defeats at the Battle of Stoney Creek and Beaver Dams. Only a small number of militia remained stationed at the Fort. Fearing an attack by the British, the Americans retreated back across the Niagara River in December, 1813. The Fort remained in British possession for the rest of the War.

An investigation into the oxidation of organic sulphides, organic selenides and simple hydrocarbons by Mortierella isabellina NRRL 1757

The work presented in this thesis is divided into three separate sections 4!> Each' 'section is involved wi th a different problem, however all three are involved with a microbial oxidation of a substrate~ A series of 'aryl substituted phenyl a.nd be,nzyl methyl sulphides were oxidized to the corre~pondi~g sulphoxides by 'Mo:rtierellai's'a'b'e'llina NRR.L17'S7 @ For this enzymic Qxidation, based on 180 labeled experiments, the oxygen atom is derived fr'orn the atmosphere and not from water. By way of an u~.traviolet analysis, the rates of oxidation, in terms of sulphox~ de appearance, were obtained and correlated with the Hatnmett p s~grna constants for the phenyl methyl sulphide series. A value of -0.67 was obtained and, is interpreted in terms of a mechanism of oxidation that involves an electrophilic attack on the sulphide sulphur by an enzymic ironoxygen activated complex and the conversion of the resulti!lg sulphur cation to sulphoxide. A series of alkyl phenyl selen~des have been incubated with the fu~gi, Aspergillus niger ATCC9l42, Aspergillus fO'etidus NRRL 337, MIIJisabellina NF.RLl757 and'He'lminth'osparium sp'ecies NRRL 4671 @l These fu?gi have been reported to be capable of carrying out the efficient oxidation of sulphide to sulphoxide, but in no case was there any evidence to supp'ort the occurrence of a microbialox,idation. A more extensive inves·t~gation was carried out with'M,e 'i's'a'b'e'l'l'i'na, this fu~gus was capable of oxidizing the correspondi~g sulphides to sulphoxi.de·s·$ Usi:ng a 1abel.edsubstra.te, [Methyl-l4c]-methyl phenyl selenide, the fate of this compound was invest~gated followi!lg an i'ncubation wi th Me isabellina .. BeSUldes th. e l4C-ana1YS1Q S-,'. a quant"ltta"lve selen'lum ana1Y"S1S was carried out with phenyl methyl selenide. These techniques indicate that thesel'enium was capable of enteri!1g thefu!1gal cell ef'ficiently but that s'ome metabolic cleav~ge of the seleni'um-carbon bond' may take plac'e Ie The l3c NMR shifts were assigned to the synthesized alkyl phenyl sulphides and selenides@ The final section involved the incubation ofethylben~ zene and p-e:rtr.hyltoluene wi th'M ~ 'isab'e'llina NRRL 17574b Followi~ g this incubation an hydroxylated product was isolated from the medium. The lH NMR and mass spectral data identify the products as I-phenylethanol and p-methyl-l-phenylethanol. Employi!lg a ch'iral shift re~gent,tri~ (3-heptafluorobutyl-dcamphorato)'- europium III, the enantiomeric puri ty of these products was invest~gated. An optical rotation measurement of I-phenylethanol was in ~greement with the results obtained with the chiral shift re~gen,te 'M.isabe'l'lina is capable of carryi~g out an hydroxylation of ethylbenzene and p-ethyltoluene at the ~ position.

The Columbian Newspaper vol. IV no. 1105- June 12, 1813

The "Columbian" was established by Mr. Holt in 1808 as an "organ of the Clintonians" (Journalism in the United States, from 1690-1872 By Frederic Hudson) and a replacement to the "Citizen". It was a passionate Democratic paper that supported both Jefferson and Madison. Holt later sold the "Columbian" to Alden Spooner, who published the Long Island "Star". The Columbian ceased in 1821. This issue includes the following War of 1812 topics: Page 2: copies of letters from U.S. Gen. H. Dearborn describing the U.S. attack on Ft. George 27 May 1813; letter from Gen. H. Dearborn describing U.S. pursuit of British troops at Beaver Dams and the U.S. capture of Fort Erie; list of U.S. killed and wounded in Commodore Isaac Chauncey's squadron in attack on York 27 April, 1813; list of killed and wounded in Commodore Isaac Chauncey's squadron in attack on Ft. George 27 May 1813; abstract of the cartel for the exchange of prisoners of war between Great Britain and the United States; mention of troop movements through New York on their way to the battle front; list of persons killed or lost on the privateer Saratoga; Page 3: account of the loss of the U.S. war ships the Growler and Eagle to the British; news from Quebec and Kingston of troop movements; U.S. ship Syren unsuccessfully pursues British ship Herald; account of a U.S. cargo ship being captured by a British military ship; account of U.S. ship Siro capturing British ship Loyal Sam; report from Halifax of recent British troop and ship movements; list of recent troop enrollments in various states; report of British troop build up in Kingston;

Boston Patriot Vol. 8 No. 13- October 24, 1812

A semi-weekly paper that began in 1809 and ceased in 1816. Its succeeding title was the Boston Patriot and Morning Advertiser. Publishers included: Everett and Munroe, 1809-Mar. 7, 1810; Isaac Munroe, Mar. 10, 1810-May 1, 1811; Munroe and French, May 4, 1811-1813; D.C. Ballard, 1814-1816. Editor: David Everett, Mar. 10, 1810-Oct. 23, 1811. Topics of interest include: Page 1: announcement of war against Great Britain and the reasons for the war; Page 2: announcement of nomination of war supporter Francis Carr for Congress; Statement of the Senate of Massachusetts in support of the war; 3 accounts of the American attack on Queenston; Page 3: report of the movement of war ships in and out of the port of Boston; news of naval movements by American and British ships; Page 4: advertisement of American and British muskets and swords for sale;

The New York Weekly Museum Newspaper, Vol. II, No.25- October 23, 1813

A weekly paper that was published from 1805 to 1814. War related news includes: Page 99 - Weekly Retrospect: American report on British naval movements near Louisiana; General William Harrison reports on: a victory at Moravian Town (Moraviantown) on October 5; Ottawas, Chippewas, Wyandots Miamies and Delaware First Nations (Indians) leaving the British side; Tecumseh remaining with the British; American army and navy attempt for a reduction of Mackinac and St. Joseph's; Colonel Chapin attacking a British picket guard near Fort George on October 6; Report that the British have abandoned the Fort George area for Kingston and is being pursued by General McClure; Forces in Sackett's Harbour ready for an attach on Canada; General Provost believed to have left Kingston for Montreal with 1000 men; Report from Burlington (Lake Champlain) of an attack on St. Armands against Colonel Clark on October 15; Report of the American's taking of the Packet Morgiana by the Schooner Saratoga under Captain Adderton by Newport; Announcement by the New York City Common Council for a celebration of Perry and Harrison's victories on the evening of October 23. The rest of the newspaper contains literary works (poems and translations), marriages, deaths and other anecdotes. The motto on the front page states: "Visiting Every Flower with Labour Meet, and Gathering all its Treasures, Sweet by Sweet."

The New York Weekly Museum Newspaper, Vol. II, No.26- October 30, 1813

A weekly paper that was published from 1805 to 1814. War related news includes: Page 103 - Weekly Retrospect: Reports on the Napoleanic Wars in Europe; Possible French and English troop movements from Europe to America and Canada; Mention of British vessels captured by American privateers Scourge, Rattlesnake and Lion; Report on New York celebration of Commodore Perry and General Harrison's victories on Lake Erie and in Canada respectively; Creek Indians attack on a supply convoy near Savannah, the provisions were recovered by General Floyd; General Harrison's account on Moravian Town (Moraviantown) and Munsey; Movements of General Wilkinson's army. Page 104 - an editorial about the madness of the times and its reflection on humanity. The rest of the newspaper contains literary works (poems and translations), marriages, deaths and other anecdotes. The motto on the front page states: "Visiting Every Flower with Labour Meet, and Gathering all its Treasures, Sweet by Sweet."

Correspondence between Mr. Monroe and Mr. Canning and between Mr. Madison and Mr. Rose

Full Title: Report of the Committee to whom was Referred the Correspondence between Mr. Monroe and Mr. Canning, and between Mr. Madison and Mr. Rose, relative to the attack on the Chesapeake : and also a communication from the President of the United States of the 30 March last, with a letter from Mr. Erskine to the Secretary of State, and a letter from M. Champagny to Gen. Armstrong Printed by R. C. Weightman