b1s.3 844 SYNTHETIC AND MECHANIL FTDE IN FLUORINE CHEMISTRY 1/1NEW DEVELOPMENTS 1..(6 CLEMSON UNIV SC DEPT OFCHEMISTRY D D DESMRRTEAU 17 RUG 83 TR- R RO 2804.5-CH

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SYNTHETIC AND MECHANISTIC STUDIES IN

FLUORINE CHEMISTRY. NEW DEVELOPMENTS IN

ORGANONITROGEN FLUORINE CHEMISTRY

Final Technical Report

Darryl D. DesMarteau

August 17, 1983

U. S. Army Research Office

Contract Number DAAG29-82-KO188

Clemson University

Clemson, South Carolina 29631

Approved for Public Release;

Distribution Unlimited

C) &rLEC T E

2 2 1983

. 09 A

83 09 Z: 028

iu 47 7 1; 371 77 N7 -7- *" * - L 7. 7 777 .- 7..

Unclass ifiedL1SECURITY CLASSIFICATION OF THIS PAGE *flen Does Fritered)

REPORT DOCUMENTATION PAGEREDNSRTISB3EIORE COMPLE~TING. FORM

1REPORT NUM13ER 2. GOVT ACCESSION NO. 3 RECIPIENT'S CATALO'., NUMBER

4. TITLE (andSubettle) S. TYPE OF REPORT & PERIOD COVERED

Synthetic and Mechanistic Studies in Fluorine Chemn- Final Technicalistry. New Developments in Organonitrogen Fluorine 20 Sept 82 - 31 May 83Chemistry 6 PERFORMING ORG. REPORT NUMBER

7. AUTNOR(s) S. CONTRACT OR GRANT NUMBERt(&)

* Darryl D. DesMarteau DAAG29-.82--K-0 188

9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT. PROJECT. TASKAREA & WORK UNIT NUMBERS* Clemson University

Department of Chemistry-Clemson, SC 29631ICONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE

U. S. Army Research Office Aa1-RPost Office Box 12211 13. NUMBEIROF PAGESResearch Triangle Park, NC 27709 9______________

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SCHEDULE

16. DISTRIDUTIO4 STATEMENT (at thApenr)

Approved for public release; distribution unlimited.

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IS. SUPPLEMENTARY NOTES

The view, opinions, and/or findings contained in this report are those of theauthor(s) and should not be construed as an official Department of the Armyposition, Policy, or decision, unless so designated by other documentation

19. IKEY WORDS (Continue en reverse side If neceeeaiy and Identify by block number)

azabutenes, oxaziridines, synthesis, polymer, polymerization, N-f lurineN-bromoimines, azaalkenes, azines, fluoride, oxidation, bromine, chlorine, fluoridepromoted reaction, additions to olef ins

S.A@8rACrfrq9ftnr a revrs sed 111 aneesyi Idewuily by block numnbee)

A series of 1,1-difluoro-2-aza-perhalo-1-butenes,CF =NCF CFXCI (X = F, Cl, Br),% ~were prepared by addition of CF=NCl to the olefins C=F X. These azabutenes

were converted in high yield to 2the novel oxaziridines 2C1XCFCF N-CF with CF 00H.

The chemistry of these oxaziridines resembles closely that previously found for% CP 't72and allows the synthesis of a variety of new fluorinated compounds.

j1* 1 143 Sotooor 00 111$*I~s 8 Ee UNCLASS r ED)________Ni5C-" IYCLASSIFIC ATIOF TIS AG (Weot& Entered)

SECURITY CLASSIFICATION OF TWOS PAGE(When Data Itnterord)

* 20. ABSTRACT CONTINUED

* The reactive perfluoromethanimine, CF =NF, previously polymerized by strongacids, was shown to also be polymeriz 2ble with the base (CH 3) 3N. Evidenceclearly indicates a homopolymer tC -N

2 n* Fluoride .promoted reactions of halogenated nitriles of the type R CN (R

CF~~~~~~ CNd adRCNr noidationCF3, 25F' C F , Cl)leads readily to R 2F 2C n F= no* of intermediate anions with the respective halogens. TAe reactivity of the

nitrogen bromine bond of the N-bromoimines can be exploited to prepare a varietyof new halogenated azalkenes by addition to both halogenated on non-halogernated

* olef ins. Photolysis of the N-bromoimines gives the respective azines,- R CF-N-N-CFR , in good yield. All of these compounds show considerable promise* for new chemistry.

0- '* C' %SSWrICA 1% N Off TMS P AG~fWhan Data, Entered)

:1 . . -. . .3

PROBLEMS STUDIED

-, Synthesis and properties of novel organonitrogen fluorine compounds were

investigated with emphasis on the synthesis of new perhalogenated oxaziridiries,

reactions of CF2=NF and SF =NF, and fluoride promoted reactions of imines and2 4

nitriles.

SUMMARY OF IMPORTANT RESULTS

1-6• Because of the fascinating chemistry of CFN-F 2,

it is of importance to prepare other homologs of this class of materials in

order to evaluate the potential of this class of compounds in general. For

this purpose it was necessary to find a synthesis of imines of the type CF2=NR.2' .

This was accomplished by a reaction of CF =NCl with CF =CFX (X = F, Cl, Br),12 2

which under the right conditions forms the respective imines.7

1700CCF =NCI + CF =CFX -a CF =NCF CFXCI*2 2 11 atm 2 2

50%

This Veaction also leads to significant formation of CF 2=N(CF 2CFX)n Cl polymers,

varying ,in properties from viscous liquids to gels and solids. These polymers

may be of interest because they still contain the reactive CF =N group.

2

With the new imines thus formed, the epoxidation was readily accomplished

by oxidation with CF3OOH, as previously used to prepare CF3A7 2 -0

CF 2-NCF 2CFx C + CPF3OOH CF 3OOCF 2N(H)CF 2CFXC1

KHF-~-4 C1XCPCF 2-CF + COF + HF22*C 2V' 2 2

80-904

4

Il - 4

These new oxaziridines are thermally stable at 22°C and show nearly the

8same remarkable reactivity as CF N-CF2.

CF (CH )C=OC 2XCFCF 2 CXCFCF2NCF ClXCFCF2N(Nu)C(O)F (Nu=C30)

0- C (CH3) 2 60C F

CF

C1XCFCF 2 9 CIXCFCF=NF + COF

CF2--- ±F2 (Nu=F)

- polymer

These series of new materials are extremely interesting and reaffirm the

industrial potential of perhalogenated oxaziridines.

Polymerization of CF =NF

We have previously discussed the novel acid catalyzed polymerization of

9the perf luoromethanimine.

ACF =NF - 4CF -N-)2 2 n

A=SbF5, CF3SO3H

This 4epresents the only known polymerization of an N-fluoroimine and this

polymer has sparked interest wherever it is discussed. In continuing work

on this material, we have investigated the polymerization of the ifiine by the

base, (CH ) N. Again, the material is readily polymerized3 3 (CH 3) 3 N ["CF2=NF ) 4CF 2 -X-) n

As yet, we have only limited characterization of the viscous liquid to solid

polymers. However 19F-NMR suggests the presence of the polymer (2 broad signals,-

area 1:2)" and mass spectra show fragments of (CF2-NF)n with n=i-3 and, depending2 n

on the ratio of (CH3)3N to CF2=NF, (CF2NF)nNMe 3 + are readily seen.

----- . . .......... .. . .. ....... .

U.,

Future plans call for a more detailed characterization of these polymcrs.

Fluoride Promoted Reactions of Imines & Nitriles

Earlier we had determined the facile oxidation by Cl and Br of fluorinated2 2

nitrogen4anions generated from imines such as CF2=NF, bv reaction with KF or CsF. 1 0

CF2=NF - CF3NF 9 - Br CF NFX2 0 3 X=ClBr 3

Extension of this work to nitriles has now been highly successful.

Br R CF=NBr (90%)

R CN R CFNX'C x

Rx CF2 Nd 2 (90%)

The N-bromoimines are particularly useful materials for a variety of useful

reactions. They readily add to a variety of halogenated and non-halogenated

olefins in high yield.

150-2000C R --R CF=NBr + - CF=N-C-C-Brx xII

>in 2 C2 F4 C2F3C , C 2 F2 C12 C2 F 3 Br, C2 F 2 HBr, C2 14 , C2 H2 F2, C 3CHCH2

They are also readily photolyzed to the azines in excellent yield.

R CF=NBr h R CF=N-N=CFR + Br2

Again, it is clear that these materials provide entry into new areas of organo-

nitrogen fluorine chemistry with obvious potential for useful new materials

ranging from novel monomers to unusual heterocycles.

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' o. 2 ° ' " ".; . . .... .a2;:' :...' -2 L I-",' ...

Conclusion. This research represents a variety of no'w developments in orvqano-

nitrogen fluorine chemistry. However we have not, closed the door on arny !p'rticular

aspect of this work. On the contrary, we have opened a floodqjatce to a wealth

-'of new ahd interesting chemistry.

7

REFERENCES

1. Falardeau, E. R.; DesMarteau, D. D. J. Am. Chem. Soc. 196, 98, 3529.

2. Sekiya, A., DesMarteau, D. D. Inorg. Chem. , i8, 919.

3. Sekiya, A.; DesMarteau, D. D. J. Org. Chem. , 44, 1131.

4. Sekiya, A.; DesMarteau, D. D. J. Fluorine Chem. , 15, 183.

5. Lam, W. Y.; DesMarteau, D. D. J. Fluorine Chem. ) 18, 441.

6. Lam, W. Y.; De Marteau, D. D. J. Am. Chem. Soc. , 104, 4034.

7. Zheng, Y. Y.; DesMarteau, D. D. J. Org. Chem. in press.

8. Zheng, Y. Y.; DesMarteau, D. D. in preparation.

9. DesMarteau, D. D. Final Technical Report, ARO, Contract #DAAG29-77-G-0071and DAAG29-80-C-0102, Nov. 30, 1982.

10. Chang, S. C.; DesMarteau, D. D. Inorg. Chem. 2, 2 805.

LIST OF PUBLICATIONS

D. Christen, H. Oberhammer, R. M. Hammaker, S. C. Chang and D. D. DesMarteau,

"The Structure of Perfluoromethanimine by Microwave, Infrared and Raman Spectro-scopy, Electron Diffraction and Ab Initio Methods," J. Am. Chem. Soc., 104,

6186 (1982).

S. C. Ch~ng and D. D. DesMarteau, "Addition Reaction of N-Bromoperfluoromethaniminewith Some Olefins," J. Org. Chem., 48, 895 (1983).

S. C. Chang and D. D. DesMarteau, "Fluoride Catalyzed Reactions of Perfluoro-methanimine. Novel Chemistry of the Perfluoromethanamine Ion", J. Org. Chem.,48, 771 (1983).

S. C. Chang and D. D. DesMarteau, "Oxidation Reactions of Perfluoromethanimineand Related Compounds. Electrophilic Additions to CF =NF and Fluoride Promoted2,,Oxidation of Perhaloimines and Nitriles by Cl and Br2 , Inorg. Chem., 22,805 (1983).

K. Johori and D. D. DesMarteau, "A Comparison of the Reactivity of CF OX(X=Cl,F) with Some Simple Alkenes, J. Org. Chem., 48, 242 (1983).

-- 8

Pa~es i Prss r Sbmited(copies previously supplied ARO)

Zheng, Y.Y.; DesMarteau, D. D., "Synthesis of 1,I-Difluoro-2-Aza-Perhalo-1-3utencsand Their Conversion to Oxaziridines", J. Org. Chem., Jan. 1984.

O'Brien,IB. A.; DesMarteau, D. D., "Some Reactions of (Fluoroimido)Tetrafluoro-sulfur", Inorg. Chem.

Zheng, Y. Y.; M4ir, Q. C.; O'Brien, B. A.; DesMarteau, D. D., "Novel Metal Fluoride*Promoted Conversion of N-Cl Bonds to N-Br Bonds. Synthesis of CF NBr and

3 2CF 3NBrCl", J. Am. Chem. Soc.

PARTICIPATING SCIENTIFIC PERSONNEL

* Dr. Darryl D. DesMarteau, Principal Investigator* Dr. Qui-Chi Mir, Postdoctoral* Dr. Brian A. O'Brien, Postdoctoral

- Mr. Yuan Y. Zheng, Visiting Scholar

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