AD-AU 655 TEXAS A AND M UNIV COLLEGE STATION DEPT OF CHEMISTRY FiG 7/3

MACROCYCLES CONTAINING TIN. TWO SYNTHESES OF ll,,6,6,11,.1.1--ETC(U)

USEP 82 M NEWCOMB, Y AZUMA. A R COURTNEY NOOO14- G-C-0584

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Technical Report 3 A b A lA sA. TITLE (amd Subtitle) S. TYPE OF REPOR " & PERIOD ZE'.

Macrocycles Containing Tin. Two Syntheses of1,1,6,6,11,11,16,16-Octaphenyl-1,6,1.,16-tetra- Technical Reportstannacycloeicosane and a Synthesis of 1,1,6,6- *. PERFORUTNO ORG. REPORT NUMBE-

Tetraphenyl-1 ,6-distannacyclodecane7. AUTHOR(*) S. CONTRACT OR GRAN NUMIER(uj

Martin Newcomb, Yutaka Azuma, Arleen R. Courtney N00014-79-C-0584

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Texas A&M University AREA & ORK UNIT NUMBERS

Department of Chemistry NR 053-714College Station, TX 77843

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Office of Naval Research Sept. 22, 1982Department of the Navy 13. NUMBER CF PAGES

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Polystanna macrocycleSynthesisPuri fi cati on

Aj 20. ASSTRACT (Continue an reverse aide It neceseary md Identfly by block numbr)

Synthetic techniques and methods for analysis and purification of macrocyclescontaining tin atoms are exemplified by the title syntheses. Highlights ofthe syntheses include a highly selective conversion of 1,4-bis-(triphenyl-stannyl)butane to 1,4-bis-(bromodiphenylstannyl)butane and atwo componentmacrocyclization which--roceeds in 43% yield to give the 20-membered ringproduct. Analytical HPLC and preparative chromatography methods for character-ization and purification of the macrocycles and their synthetic intermediates

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HSPll l~ oeJt l

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and analogs are described. Other syntheses which show the generality of :.emethods are discussed.

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TECHNICAL REPORT NO. 3

Macrocycles Containing Tin.

Two Syntheses of

1,1,6,6,11,11,16,16-Octaphenyl-1,6,11,16-tetrastannacycloeicosane

and a Synthesis of

1,1,6,6-Tetraphenyl-1,6-distannacyclodecane

by

Martin Newcomb, Yutaka Azuma, and Arleen R. Courtney

Texas A&M UniversityDepartment of ChemistryCollege Station, TX 77843

Sept. 22, 1982

Reproduction in whole or in part is permitted forany purpose of the United States Government

* This document has been approved for public release

and sale; its distribution is unlimited

* This statement should also appear in Item 10 of Document Control Data- DD Form 1473. Copies of form available from cognizant contractadministrator.

'.acrocycles Containing Tin. Two Syntheses of 1,1,6,6,11,11,16,16-

Octaphenyl-l,6,11,16-tetrastannacycloeicosane and a Synthesis of

1,1,6,6-Tetraphenyl-1,6-distannacyclodecane

Martin Newcomb*, Yutaka Azuma, and Arleen R. Courtney

Department of Chemistry, Texas A&M University, College Station, Texas 77343

Sum ary: The title syntheses are described. The synthetic and Duri"ica-

tion and analytical methods employed are of general utility for the

preparation and functionalization of members of this class of c-,w!)o,,rds.

Macrocyclic, polydentate cation-complexing ligands (crown ethers,

cryptands, etc.) have enjoyed a broad and useful chemistry during the

past decade and a half, but their counterparts, anion-complexing m3,ro-

cycles have received relatively little attention. Recent advances n

anion comDlexation, including structural selectivity, by macrocycliL

polyammonium ligands suggest that this will be a fertile area of sttdy.2

Reasoning that oolystanna macrocycles may be appropriately substit-ed

to give Lewis acid cor;olexinn ligands which are direct analogs of rown

ethers or cryptands, ..,e 'have develoned synthetic procedures far this

class of compounds represented by the title compound (.). Two approaches

(Scheme) have yielded the target 20-membered ring compound. The s~nthetic

methods and purification techniques described herein are generally

applicable for this class of comoounds and also furnish tin function~lized

macrocycles. We are unaware of other neutral macrocycles with the

notential for anion cownlexation.

2

A!I reactions were run in argon or nitrogen atmospheres. Treat+ent

of the diGrignard reagent from 1,4-dibromobutane with triphenylstanryl

chloride in tetrahydrofuran (THF) gave 1,4-bis-(triphenylstannyl)-

3a b 0butane (?. mp 148.5-149 C) in 77% is)iated yield after

recrystallization from hexane--dichlorompthane (2:1, v:v). Unacceptably

low selectivity was observed in several attempted conversions of 2 to

1,4-bis-(bromodiphenylstannyl)butane (3) with var.ious reagents and

conditions; a second phenyl grouD was readily replaced giving the

dibromophenylstannyl moiety. However, treatment of 2 with 2.1 molar

equivalents of hydrogen bromide in dry dichloromethane at -78 0C

followed by slow warming to room temperature gave, a, ter recrystalliza-

tion (dry ether), 33a in75% yield (mp 88-90 °C). The dibromide 3 wai.

treated with excess 4-chlorobutylmagnesium bromide in THF at -10 0C

for 1.5 h followed by warming to room temperature (7 h) to giv2

1,14-dichloro-5,5,10,10-tetraphenyl-5,10-distannatetradecane ")3a

which was purified by reverse phase chromatography (C-18, met'ianol

elution) in 62% yield (oil).

The two component macrocyclization was accomplished at hich dilt-

tion. The dibromide 3 was added to excess lithium metal in TIF to g ve

the dilithium reagent 5 (total base = 63% of theory). A THF ;olutior

of 5 (diluted to 0.037 M) was added slowly (2 h) to a TdF solution of

4 (1.0 molar equivalent, 0.02 M) at 0 °C followed by warming co room

temperature (12 h). After a conventional work-up, the crude product

was purified by reverse phase chromatography (C-18) with THF--azetonitri :'

elution (1:3, v:v) to give the desired macrocycle 1 in 43% isolated

yield (mp 107.5-108 °C from hexane--ether, 3:1).

- -. ~.

3

Alternatively, macrocycle was also obtained in lower yit'd Fro,

a high dilution, four component Pacrocyclization reaction. This, the

diGrignard reagent from 1,4-dibromobutane in THF (0.07 Y) was added over'

2 h to one molar equivalent of dibromide 3 in THF(O.034 M) at 0 °C.

After 12 h at room temperature, the reaction was quenched and worked up.

The crude products were purified by preparative reverse phase chroma-

tography as above to give, after recrystallization, the desireJ !,iacro-

cycle $. in 16, yield and 1,1,6,6-tetraphenyl-1,6-distannacycodi.jcdne a''

( pi rp 114-114.5 °C, lit. 4 mp 96-98 °C) in 10% yield. Cuipound 6 has

been prepared by a different route.4

The macrocycles 1 and 6 may be analyzed readily by analytical HPLC

(reverse phase, C-18) with methano' elution; the 10-membered rino com-

pound 6 elutes before 1. However, for preparative chromatography, the

solubilities of 1 and 6 in methanol are inconveniertly lo%. Thus,

chromatography with the mixed solvent system THF--&cetonitrile was

developed. We found that analytical HPLC on 10 'pheriscrb ODS columns

correlated well with preparative chromatography on 40 p ODS supplied by

J. T. Baker Co.; the analytical phase retained material about 1.5 times

as long as the preparative phase in terms of column volumes.

' If

4

The procedures described auove are generally useful for the prepara-

tion and functionalization of other tin conaining. macrocycles. For

example, the reactions of the 6-, 8-, and 10-carbon analogs of with

the corresponding chaii length u,w-diGrignard reagents gave the 14-, 18-,

and 22-membered ring Lnalogs of the distanna compound , resoective'y,

as well as low yields of the 28-, 36-, and 44-membered ring analogs of

tetrastanna compound , tespectively. All separations were accomplished

by reverse phase chromatography. Further, when tie selective brorlinatio',

procedure was applied to macrocycle 6, we obtaineJ 1,6-dibromo-1,6-dipaheny'-3a

1,6-distannacyclodecane; this reaction exemplifies a critically important

functionalization of the macrocycles. Finally, preparative reverse phase

chromatography of the intermediate tin bromides i; also possible on a

C-18 column with THF--acetonitrile elution if dry solvents are used.

As in any macrocyclization reaction, the high dilution methods we

used required careful technique. However, n our minds, the key steps

to obtaining macrocycle I were the selective brom:nation of 2 and our

development of a preparative chromatography methol. The two component

macrocyclization route and reverse phase proparat ve chromatography

permit the synthesis of 1 in grain batches. With -he methods at hand

we plan to prepare and functionalize severd' members of this class of

compounds and explore their application ir. anion coordination chemistry.

Acknowledgement: This work was supported by ;he Office of Naval

Research.

I

.................

5

References and Notes

(1) Camille and Henry Dreyfus Teacher-Scholar, 1980-1985.

(2) Dietrich, B.; Hosseini, M. W.; Lehn, J. M.; Sessions, R. B.

J. Am. Chem. Soc. , 103, 1282; Hosseini, M. W.; Lehn, J. M.I.

J. Am. Chem. Soc. 82, 104, 3525; and references in each.

(3) (a)The compound was characterized by H NMR spectroscopy; (b) the

compound was character- zed by 1H-decoupled 13C NMR spectroscopy

and by osmornetric molecular weight determination; (c) a satisfactory

elemental ana'ysis (±0.41 for C, H) v~s obtained.

(4) Davies, A. G.; Tse, M. -W.; Kennedy, L'. D.; McFarlane, W.; Pyne,

G. S.; Ladd, M. F. C.; Povey, D. C. J. Chem. Soc., Chem. Commun.

It8, 791.

I

Scheme

Br~g rvgBr +Ph SnCl Ph Sn -''-fh 3

HBr

Dh S- 7 '-\-SnPh < CI(CFI2)4VMger Ph Sn-/">\,-Sfl-Ph2

B r SBr

4"' Ct Li

Ph2Sn -"/-- SnPh2 9 gg

1 +Ph Sn SnPh2

Ph2Sn ~NSnPh 2

Supplementary Information for Feview Purposes

Osmometric Molecular Weight Determinations.

Compound MW Calcd MW Found

755 734

1 1315 1341

6 657 654

Elemental Analysis of Compound .

C64H72Sn4 : %C calcd 58.38, found 58.06; ",H calcd 5.52, found 5.43.

*i.

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