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LIANG, Wei Chuan, 1936- STUDIES ON VINYL CATIONS AND UNSATURATED CARBENES.

The Ohio State University, Ph.D., 1972 Chemistry, organic

University Microfilms, A XEROX Com pany , Ann Arbor, M ichigan

THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. STUDIES ON VINYL CATIONS AND UNSATURATED CARBENES

DISSERTATION

Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University

By

Wei Chuan L iang; B .A ., M.S.

# ir -/c ir %'c

The Ohio State University

1972

Approved hy

A dviser DepartmenL of Chemistry PLEASE NOTE:

Some pages may have

i nd i St i net print.

Filmed as received.

University Microfilms, A Xerox Education Company DEDICATION

To ray parents

IX ACKNOWLEDGMEIW

The author "wishes to express his sincere gratitude to Professor

Melvin S. Ne"wman for his constructive criticism , guidance, and en­ couragement throughout the course of this research, and for his generous assistance in the preparation of this manuscript.

And a special thanks is due to the author's wife, Yu-Lan, for her untiring patience and support.

i i i VITA

November 2$, 1936 ...... Born, Shanghai, China

1961 ...... B.A., Kalamazoo College, Kalamazoo, M ichigan

1 9 6 1 -1 9 6 7 ...... Research Chemist, The Luhrizol Corporation, W ickliffe, Ohio

1966 ...... M.S., Case-Western Reserve University, Cleveland, Ohio

1 9 6 7 -1 9 7 2 ...... Teaching Assistant, Research Assis­ tant, Research Associate, and Teach­ ing Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio

IV TABLE ΠCONTENTS

Page

DEDICATION...... i i

ACKNONIEDGKiENT...... i i i

VITA ...... iv

LIST OF TABLES ...... v i i

LIST OF FIGURES ...... v i i i

LIST OF SCimUES ...... ix

INTJ^OjJUCî IOÏÏ ...... 1

HISTORICAL ...... h

DISCUSSION OF RESULTS ...... 52

EXPERII'ffiNTAL...... jh

Generalizations ...... 74

Alkaline decompositions of 5-methyl-5-t-tutyl-N- nitroso-2-ozazolidone ( 3 ) ...... 75

Preparation of N-nitroso-4;5,5-trimethyl-2-oxazoli- done (40) ...... 79

AUtaline decomposition of N-nitroso-4;5;5-trimethyl- 2-oxazo].idone (^ ) ...... 85

AUuiline decomposition of 1-(N-nitrosoacctylaminomethyl)- cyclohexanol ( 6 1 ) in the presence of ketones ...... 92

AUcaline decomposition of l-(N-nitroooacetylaminomethyl)- cyclohexanol ( 6 1 ) in the presence of aldehydes ...... 96

Preparation of cyclohexylideuemethyl t-hutyl ketone ( 6 9 ) ...... 100 Page

Decomposition of 1-(N-nitrosoacetylaminomethyl)eyclo- hexanol (^ ) vrith triethylamine in the presence of iso­ butyraldéhyde ...... 104

Alkaline decomposition of 1-(N-nitrosoacetylamino- methyl)cyclohexanol ( 6 l) in the presence of nucleo­ p h ile s ...... 10^

Alkaline decomposition of 1-(N-nitrosoacetylamino- methyl) cyclohexanol (^ ) in the presence of triethyl phosphite and acetone ...... I l l

Alkaline decomposition of 1-(N-nitrosoacetyl'^.mino- methyl)cyclohexanol (^ ) in the presence of trialkyl phosphites ...... 112

Decomposition of 1-(N-nitrosoacetylaminomethyl)cyclo­ hexanol (6l) •'.rith pyrrolidine ...... U 4

Decomposition of 3i-nitroso-l-oxa-$-azaspiro[4; 5]decan- 2-one (^ ) in diethylamine ...... 115

AUcaline decomposition of 5“i^itroso-l-oxa-3-azaspiro- [4,5]^ecan-2-one (^ ) in the presence of cyclohexene and a phase transfer agent ...... U 6

AUcaline decomposition of 3-nitroso-spiro[fluorene-9S 5- oxasolidin]-2-one (74) in the presence of cyclohexene ... U6

Preparation of 3-acetylamino-2-methy1-2-butanol ( t6) .... 117

Preparation of methyl n-butyl-N-chlorocarbamate (t 8) .... H 8

AUcaline decomposition of methyl n-butyl-N-chlorocarba­ m ate (7 8 ) in the presence of cyclohexene ...... I I 9

AJJcaline decomposition of methyl n-butyl-N-chlorocarba­ mat e (7 8 ) ...... 119

V i LIST OF TABLES

T ab le Page

1. AUcaline decomposition of 5? 5-dialkyl-3-nitroso-2- oxazolidones (l) in the presence of halide ions ...... 6

2. AUcaline decomposition of 5^5“dialkyl-3-nitroso-2- oxazolidones (l) in the presence of olefins ...... 12

3. AUcaline decomposition of 5"i^nsthyl-5-t-hutyl-3-nitro30- 2-oxazolidone ( 3 ) with sodium phenoxide in phenol-glyme ... 38

4. AUcaline decomposition of h-nitroso-4,3;3-trimethyl-2- oxazolidone (^ ) ...... 44

5 . AUcaline decomposition of 1-(N-nitros oacetylaminomethyl)- cyclohexanol (^ ) in the presence of ketones and alde­ hydes ...... 49

6. Alkaline decomposition of 1-( N- nitros oacetylami nomethyl)- cyclohexanol ( 6 1 ) in the presence of nucleophiles ...... 60

VI1 LIST OF FIGURES

Figure Page

1. Wmr spectrum^ 60 Mz, of ^ in CCI 4 ...... 77

2. Infrared spectrum of ^ ...... 80

3 . Nmr spectrum; 60 MIZ; o f ^ in CCI 4 ...... 8 l

4. Infrared spectrum of ...... 82

5 . Wmr spectrum ; 60 MIZ; o f ^ in CCI 4 ...... 83

6 . Infrared spectrum of ^ ...... 87

7 . Infrared spectrum of ^ ...... 88

8 . Wmr spectrum; 60 I4HZ; of ^ in CCI 4 ...... 89

9 . Infrared spectrum of ^ ...... 91

10. Infrared spectrum of % ...... 95

11. Infrared spectrum of ^ ...... 97

12. Wmr spectrum; 60 MIZ; o f ^ in CCI 4 ...... 98

1 3 . Infraj.’ed spectrum of 02 ...... 101

14. Wmr spectrum; 60 MIZ; o f % in CCI 4...... 102

1 5 . Infrared spectrum of azidoraethylenecyclohezane ...... IO6

1 6 . Wmr spectrufi; 60 MiZ; of azidomethylenecyclohezane in CCI4 ...... 107

1 7 . Infrared spectrum of cyclohezylidenemethyl thiocyanute ... IO 9

1 8 . Wmr spectruii; 60 MIz of cyclohexylidenemethyl thio- cyanate in CCI 4...... 110

1 9 . Wmr spectrum; 60 MiZ; o f JO in CCI 4 ...... 113

VI1 1 LIST OF SCHEMES

Scheme Page

1 ...... 3

II ...... 5

III ...... 9

IV...... 13

V...... 18

V I ...... 22

VI I ...... h2

V II I ...... 49

IX ...... 51

X...... 52

X I ...... 57

X II...... 66

IX INTRODUCTION

1-4 The intermediacy of either a vinyl cation or an unsaturated car'-

(1 ) M. S. Nes'mian and A. K utner^ J . Amer. Chem. S o c ., T^, ( l 9 5 l ) .

(2 ) M. S. Neinnan and C. D. Beard, ibid., 9,1, 9^77 ( 1 9 6 9 ).

(3 ) M. S. Neiman and C. D. Beard, ibid., ^ 4309 (197O ).

(4) M, S, Neuman and C. D. Beard, ibid., £2, 7564 (l970).

2, 3,5-8 bene has been postulated to explain the products obtained from

( 5 ) M. S. Nevman and A. 0. M. Okorodudu, J. Oiy;. Chem., 3jb 1220 ( 1 9 6 9 )

(6 ) M. S. Newian and T. B. P a tr i c k , J . Amer. Chem. G oc., 9 I , 6 4 6 l ( 1 9 6 9 ) . ^

(7 ) M. G. Neinnan and T. B. Patrick, ibid., 4312 (l970).

(8) M. S. Nemian and C. D. Beard, J. Or^. Chem., 2412 (l970).

the base induced decomposition of 5;5-disubstitutcd-N-nitroso-2-oxa% oli- dones.

R \ © C = C-1I R \ ( •0 / \ R C = 0 / -N -NO 0 = 0: R 2

In a sim ilar study N-nitrosoacetylaminoalcohols were decomposed in base to g iv e products which were also explained by the intermediacy of an unsatm'ated carbene.

Typical reaction products are shoim in Scheme I.

The objective of this work was to study the stereochemistry of products resulting from an unsymraetricai. vinyl cation or an unsymmetrical unsaturated carbene; to study the reactions of a nitroso coirpound which could not conceivably proceed through an unsaturated carbene interme­ diate; and finally to explore new chemistry on the alkaline decompositj.on of N-nitrosoacetylaminoalcohols. Scheme I + C6H5OCH3

PhO^ PhOH glyme X = C l,

R \ ( - 0 , / R \ 0 = 0 CH2 — R NO

R ’OH

© 0

R ^ R \ / S i( E t) ; C=C / N R OR’ R H

». C = C = C 0]lt R II HISTORICAL

Since the isolation of a high yield of cyclohexanecarhoxaldehyde from the alkaline decomposition of $-nitroso-l-oxa-3-azaspiro[4;^]decan- 9 2-one, further work on this reaction has heen done in these laboratories.

(9 ) M. S. Netraian, J. Amer. Chem. Soc., 71, 378 (19^9).

1 Ne'vraian and Kutner shoived that the alkaline decomposition of 3- nitroso-2-oxazolidones (l) gave a variety of products on changing the substituents and the base.

I I CÎI2 — N-NO

(1)

If the Ri and Rg groups were aliphatic, aldehydes RiRgCIICHO were formed. If the R% and Rg groups were phenyl, a quantitative yield of diphenylacetylene \ras obtained. If the reaction was carried out in absolute alcohols using sodium ethoxide as base, vinyl ethers were ob­ tained in good yields. A mechanism (see Scheme II) which involved the vinyl cation as a key intermediate \ras postulated to account for the products. Thus, the nucleophilic attack by water or alcohols on the Scheme I I

R i, R i. 0 OH / Rs C — 0 Rg C-OH / C H a — N - W O

(1)

0 0 II R i. II HaO R i 0 - C - OH ;c — 0 - c — OH / © Rs Ra^ CHa—N=N- 0 ' A CHa-N = N ^ OH

© -OH

0 ^ II + Rl^ (To-C-OH © ,OH R i. 0 = 0 0 / ^ C H -N a® Ra H -H O -C - 0©

©OH

-Np

R l .V, © PRODUCTS C-C-H Ra (2 ) vinyl cation 2 yielded aldehydes or vinyl ethers and the migration of

Ri or Rg gave acetylenes.

V/hen 5^ 5“<3-iaHo/-l-3-nitroso-2-oxazolidones (l) vere decomposed m th a hase in the presence of a large excess of halide saltS; good yields 2 ,3 of vinyl halides vere obtained (see Table Ij. The authors assumed

T ab le 1

Alkaline decomposition of 5; 5“dialltyl-3-nitroso-2- oxazolidones (l) in the presence of halide ions

R i.

Ra ( 1) / CHg—N — NO

a Ri Ra P ro d u c t£ ^ Y ie ld

“ (CHa)s“ 82

o

78

I - ( 0112)4 - 81

CH3 CII3 0 = 0 80 a. Lithium 2-methoxyethoxide vas used as the hase. A saturated solution of halide of sodium or lithium in 2-raethoxyethanol vas euployed. 7 that the vinyl cation 2 was involved, although they did not rule out the possibility of an unsaturated carbene intermediate.

In order to test the stereoselectivity in the reactions of an un­ symmetrical vinyl cation, the alkaline decomposition of ^-methyl-^-t- butyl-3-nitroso-2-oxazolidone (3) under similar conditions \ras examined.

The ratios of isomeric products are shoim below.

(CH3)sC c ----- 0 ^ NaOCHsCHsOCHs CH3 / C = 0 EOCHpCEpOCHs (C E s^ sC ^ / + Wax C=C^ C E g— N -N O CEa X

(3 ) X = I 94 X = Br 93

(C H 3)3^ / X + c = c C Es^ E 6 7

These results were interpreted as the consequence of the preferred halide ions attack from the unhindered side of the unsymmetrical vinyl cation.

(C H 3)sC ^ 0 (CE3)3C.^ C=C-E > C — A X

Treatment of 3, 5-dimethyl-3-nitroso-2-oxazolidone (4) in glyme \rith 4 sodium phenoxide in the presence of phenol offered new proof for the 8 existence of a vinyl cation intermediate. Instead of obtaining the ex­ pected high yield of 2 -m e th y l- 1-propenyl phenyl ether (^) there were ob­ tained high yields of anisole ( 6 ) and 2 -methoxyethyl 2 - m e th y l- 1 -p ro p e n y l e th e r (t). To account for the unexpected cleavage of the solvent in this reaction the authors postulated that the vinyl cation 8 was formed from 4 and complexed with the oxygen atom of glyme to give the oxonium s a l t 9 , which was then attacked hy the phenoxide ion to yield the pro­ ducts as shoim in Scheme III. As cleavage of ethers hy carhenes only lo take place under pyrolytic conditions; the experimental results strongly

(lO) W. Kii'mse, ^'Carhene Chemistry,’’ Academic Press, New York, N.Y., 19 6 4 , pp 3 6 -T , 6h, 10 7 - 8 , contains references for ether cleavages hy cai’henes.

supported that a vinyl cation was involved and not the unsaturated car- h en e.

( 1 1 ) See Scheme II for the mechanism leading to 8 .

X2 I n 1964 nine suggested in his hook a different mechanism which in-

( 1 2 ) J. nine, “Divalent Carhon, ” Tlie Ronald Press, New York, N.Y., 196 ^1, pp 89 - 9 0 .

volved an unsaturated carhene ^ to account for the products from the alkaline decomposition of 5“Suhstituted-^-nltroso- 2 -oxazolidones (l). Scheme I I I

C E s^ .H (5) c=c X m inor C E 3 OCsEs p ro d u c t

C H 3 s e v e ra l 0 . ste p s^ ^ CSa^ © C H 3 c=o C-C-H / CE3 CEg — N -NO

CE3OCE2CE2OCE3 (4) ( 8 )

E H + CgEgOCEa C—C ^ 0 c=c \ C E a^ 0-CE2CE20CE3 CE3 ÿO-CE2CE20CE3

CE3 L (T) (6) CsBsC©

(9)

VO 10

0

Ri^ ^O-C-OH -H2 CO3 Rg^ '^CHsN-NGH Rg^ ^N=N-OH

-H2 O

R i N. E l "V C = C: ■Z-%, 0 = 0 = % R? Rp

( 1 0 )

13 Our tin and covrorkers also postulated the unsaturated carbene as

(1 3 ) D. Y. Ourtin; J. Kanqinieier, and B. R. O'Oonnor^ J. Amer. Ohem. Soc., 87, 863 (19G3).

a possible intermediate for the formation of diphenylacetylene from the deamination of the vinyl amine 11.

P h ^ Ph^ H Ph. \ 0 = 0 ^ 0 — 0 =l\f2 P h ^ N =N -O H P h '

(Id.)

-N.

Ph rearrangement \ PhO = CPh 0 = 0: Ph' 11

The addition of carhenes to olefins has heen used as a criterion 14 to establish the formation of these intermediates. In 1965 Tanahe and

(1 4 ) W. Von E. D o erin g and A. K. Hoffman, J . Amer. Chem. S o c ., 618 2 ( 19 5 ^+); P. S. Shell and A. Y. Garner, ihid., 78, ^^90 U996); H. D. H a r ts 1 e r, ihid., 8 ^ , 4990 ( 1 9 6 1 ).

( 1 5 ) M. Tanahe and R. A. Walsh, ihid., 8^, 3522 ( 1 9 6 3 ).

15 Walsh reported the formation of methylenecyclopropanes hy the reaction of vinyl halides \fith potassium t-hutoxide in olefins. By using methyl 16 lithium as hase Harts1er reported the same kind of products. Both

( 1 6 ) H. D. H a rts 1 e r, J . Amer. Chem. Soc., 66, 526 (1 9 6 4 ).

groups assumed the unsaturated caahenes 10 to he the intermediates.

-K ’’"-'0 = 0: -0 Eg ^ C l R2 ^

( 1 0 )

When 5 ) 5- d.io.ll'cyl- 3- n itr os o- 2- oxasolidones (l) uere treated with allcoxides in the presence of olefins methylenecyclopropanes \rere oh-

5 , 6 tained (Tahle 2). The authors proposed a mechanism uhich involved the unsaturated carhenes 10 to explain the products (Scheme IV).

The formation of 9-(methoxymethylcne)-fluorene from the decomposi­ tion of 3“î^itrosospiro[f].uorene-9', 5"Oxasolidin]-2-one vith 50^ potassium T able 2

Alkaline decomposition of 5,5-dialkyl-5-nitroso-2-oxazolidones (l) in the presence of olefins

R i Ra Olefin Product fo Y ie ld

- ( C E s ) 5- H I < J 65 O CÏÏ3

CH3 CHs (083)20=0(053)2 = 21 083"^ '"0 CH3

CH2 =CH-Ph = 5 2 C8 3 / ^ 0 8 2

0 5 3 ^ C=C h3 0 8 3 ^

K) 15

Scheme IV

0 0 0 II II Ri ^O-C-OEt .0-0 - OEt LiOIît / © - G- 0 R2 CH2 -N-WO Rg^ CHg-Ng'"

( 1) 0 II -EtOC - OH

© - i P B i Ng 0 = 0 =Ng <------0-0 R g ^ ^H

( 1 0 )

E4 ^ '^Bg

B s . /B 4

:%:L l4 17 hydroxide in methanol vas explained in terms of a vinyl cation inter-

( 1 7 ) M. S. Wetnuan and A. E. Weinberg; J. Amer. Chem. Soc., 7 8 ; ( 1 9 5 6 ).

mediate. HOTrever, when 3-nitroso-l-oxa-^-azaspiro[4;$]decan-2-one (l2) was treated with lithium ethoxide in a mixture of ethanol and cyclo- 5 hexeno; both vinyl ether and methylenecyclopropane were obtained. The

unsaturated carbene was suggested as the common intermediate to account

0 LiOEt / \ + OCI E t OH) \ / \ cyclohexene

( 12) for the products. The vinyl ether could be formed by the insertion of 10 the unsaturated carbene into the O-H bond of ethanol. Treatment of

( 1 8 ) The formation of ethers by reaction of carbenes with alcohols hac been reported by R. M. G. Hair; E. Meyer; and G. W. Graffin; Angew. Chem. I n te r n . Ed., 46$ (1 9 6 8 ) and references therein.

12 with dry sodium methoxide in CH3OD gave vinyl ether 1$ with the methylene hydrogen being mainly deuterium. No incorporation of deuterium

OCH3

II

(1 3 ) (14) 15

vas detected at the methylene position vhen vas treated "vrith sodium

methoxide in CH3OD. Furthermore, vhen 12 vas treated vith insufficient

sodium methoxide in CH3OD, the 12 isolated after partial reaction did

not shorvr any incorporation of deuterium. Although these experimental results strongly suggested that the unsaturated carhene vas the interme­

diate, there remained a possibility that deuterium exchange of some

intermediate prior to the formation of the unsaturated carhene or vinyl

cation might have occurred. 19 Carbonium ions abstract hydride ion from trialkylsilanes, vhile 20 carbenes insert betveen the silicon-hydrogen bond of triallqylsilaiies.

(1 9 ) F. A. C arey and II. S. Trem per, J . Amer. Chem. S o c ., ^0^ 2578 (1968); 2^ 2967 (1969).

(20) D. Seyferth, J. M. Bui’litch, II. Dertouzos, and H. D. Simmons, Jr., J. Organomctal. Chem., 7, ^1-05 (1967); D. Seyferth, R. Damrauer, J . y .- P . Mui, and T. F. J u l i a , J . Amer. Chem. S o c ., 90, 2944 ( 1968).

The formation of vinyl silane 1^ from the alkaline decomposition of 4 in the presence of an excess of triethylsilane vas therefore assumed to go 2,3 througli an unsaturated carbene intermediate.

C IIs^ 0 ■ — ^ (11)38 ill CH3 II -N-NO

(4 ) (15) l6 7 The alkaline decomposition of 3 in triethylsilane yielded pre­

dominantly (lO:l) the cis isomer l6. This result was explained hy

(CH3 ) 3 C. _ (013)30. ,Si(Et )3 (0 1 3 )3 0 ^ C =C : 0 = 0 + 0 = 0 0H3^ 0H3^ H 0H3^ Si(Et)3

(1 7 ) (16) ( 3â )

c is tr a n s

assuming that the luisymmetrical unsaturated carbene ^ abstracted a

hydride ion from the less hindered side to form an ion pair as the

initial step. The collapse of the ion pair yielded the major product

16. Thus the insertion of the unsaturated carbene to the silicon-hydrogen

bond appeared to be stereoselective.

(053)30. 0 (053)30. C) yrv , (053)30^ S i ( E t )3 0 = 0: —> ^0=0% smEt)3 > 0=0 0 5 3 ^ A OH3 OHa"' H

S S iE tg

(17) (18) (16)

When h was decomposed with sodium alkoxides in the presence of

8 ethoxy acetylenes allenic acetals were isolated instead of the exj)ected

substituted methylenecyclopropenes. A mechanism (Scheme V) was postu­

lated to account for the observed products. Methyleneeyelopropene (25) 21 was assumed to be a labile species. The attack of the alkoxide ion on IT

OEt CH3 I "c 0 V •^1'^RiC%P ^ CHs^ /CH-ORi/ ( C H 3 ^ ^ + RCsCOEt ^ C=C=C.

CH2 E —NO

(4) R-H; Ri=Rt ( 2 0 ) 35^

R=H; R1-CH3 ( 2 1 )

R=CH3; R i-E t (2 2 ) 37^

(21) Examples of the addition of bases to cyclopropenes are K. B. Wiberg, R. K. Barnes, and J. Alb in, J. Amer. Chem. Soc., TO, 499^ (1957); T. 0. Shields and P. D. Gardner, ibid., tip, 9425 (Ï967); G. L. Gloss in ''Advances in Alicyclic Chemistry, ’ Vol I, H, Hart and G. J. Karabatsos, Ed., Academic Press, New York, N.Y., 1966, P 8 3 .

25 yielded ^ which was then protonated to give and 22. Alter­

natively ^ could rehybridize to give ^ which then reacted with alcohols to give the products.

Recently an improved method of generating unsaturated carbenes which involved the treatment of N-nitroso acetylaminoalcohols with base 22 23 by means of Phase-Transfer Catalysis was reported. An example is

(22) C. M. Starks, J. Amer. Chem. Soc., 195 (l97l).

(23) M. S. Newman and Zia ud Din, Syn. Commun., l(4), 247-251 (l97l).

given. The advantages of using this type of carbene precursors were the 1 8

Scheme V

0 C H 3 . C H s^ 0 © C = C : + R i O M C H 3 / 0 ^ C H 2 - N - W O EC=C-OEt

( ^ ) (it)

CEs. ,CIl3 C a CH3 ^ 0 -, C = C ^ />© CH3 "^ C = C—ORb R ^ ^ '^OEt

O R i (A)

( ^ )

a

CH3 . ,.CH3 C H 3 . C — OEt 'C = C = C ^ CH3* ^ ^ R c II (g r) C ^ G /O R t R C b R i O H

O R i /

(26) (æ), (21), (22) 19

- ?" + 60^ Aliquat 336^^ 0

(24) Aliquat 33^ is methyl tricaprylylammonium chloride obtained from G en eral M ills C hem icals ^ Kankaicee^, 111.

high yields of the products and the relatively lov? temperature (-10°) at which one could carry out the reactions.

In the present work 1-(N-nitrosoacetylaminomethy1)cyclohexanol was decomposed with base in ketones, aldehydes, sodium azide, potassium thiocyanate, and trialkyl phosphites respectively. Some of the related reactions as well as preparative methods for products similar to those

obtained from the present study but done in other laboratories are reviewed in the following section.

Reactions of Carbenes with Carbopyl Compounds.

Photolysis of diazomethane in acetone with light of wavelength 25 > 5200 A yielded four major products: 2-butanone, 2,2-dimethyloxirane,

(25) J. N. Bradley and A. Ledwlth, J. Chem. Soc., 5480 (1965).

2-methoxypropene, and 2,2, ^4,4-tetram ethyl-l,5-dioxolane. With the excep­ tion of 2-butanone which was explained by a direct carbene insertion 20

into a C-H bond.; the remaining products were thought to he derived from

the dipolar intermediate 28.

0 h v 0 II > 3200 Â II © © C H 3 - C - CHs + CH2N2 CÎÎ3CH2C-CH3 + (CH3)2C^ CH2 0

C I I 3 CH3COCH3 0 OH. 0 , J c;^ CH3^ CH3

© © (053)20. CH2 -> 052=0-00113 I 0H3 ( 28)

053 Or -052 053^ '^ 0 '^

Copper-catalyzed decomposition of diazoacetate in the presence of 26 benzaldehyde gave predominantly l,3 “dioxolane. Again, the 1,3-dipolar

(26) R. Huisgen and R. Bermes, Angew. Chem., 63O (1965).

species (29) was postulated as the intermediate. 21

Cu NgCHCOgEt % + HCCOsEt 80°

HÜCOgEt + PhCHO CHCOgEb H ^ © © ( 2 9 )

PhCHO

C CHCOgEb \ I 91^ 0-C H Ph

27 Ethyl diazoacetate has heen reported to react vith acetone to

(2T) M. s . Khar as ch, T. Rudy, W, Nudenherg, and G. Buchi, J. Org, Chem., 1& 1050 (1955).

yield a variety of products. The formation of these products -vras ex­ plained hy the carhoethoxycarhene ^ attack of the carhonyl oxygen to give the 1,3-dipolar intermediate By a proton shift gave enol ester from vhich ^ vas derived hy further addition of The reaction of ^ trith another molecule of acetone yielded ^ (Scheme Vl),

An enol ether >ras obtained as the major product vhen henzosuher- 28 one vas treated vith ethyl diazoacetate and copper povder. 22

0 Cu CHsC - CH3 + MgCHCOgEt CH2= ^ C - 0 - CHgCOzEt 90° I C H 3 24#

(30)

C H 3 . O x , + C H 2 - C - 0 -CH-COalît + (013)20 CH-C02Bk I I I HO-0(013)2 0 ------C(CH3 )2

(3 1 ) ( 3 2 )

9#

CH3 I + 0 I2 ,C -0 -CH2C02Et 23# H ' COaEt

(33)

Scheme VI

013 © 013 ■> CH2 = C - 0 I3 C I Ov. .0 0 X CH2C02E t OICOgEb ©

■ : CH- COgEk ( 5 5 ) (3 0 )

(34)

C I I 3 C O C I I 3 : CH-C02E t f

( 3 2 ) (33) 23

(28) c. D. Gutsche and M. Hillroan, J. Amer. Chem. Soc., 22^6 (l95^)*

^CHgCOgBb

NaCHCOsEt + ) | ^ ) (5 0 .5 ^ )

Interestingly-; oxiranes were not among the products of ethoxycar- honyl carhenoid reactions. However, the addition of bis(trifluorom ethyl)- 29 carhene to difluoro ketone gave perfluoroisohutylene oxide in yield.

(29) W. I4ahler, J. Amer. Chem. Soc., jgO, 523 (1968).

C F s^ F F

Highly fluorinated ketones also formed oxiranes with dichlorocarbene 30 generated by heating PhHgCClaBr.

(30) D. Seyferth and W. Tronich, J. Organometallic Chem., 8 (1969).

ClFaC Cl PhllgCClaBr + (CFaX)aCO ------^ C ----- ClFgC^ ^0 01

X = C l; F 2h

Dihalocartenes generated from haloforms and base have a tendency

to attack the enolate ions of carbonyl compounds, followed by dehalo- 31 genation whenever possible. Some of these results are illustrated by

(31) T. Y. Shen, S. Lucas, and L. H. Sarett, Tetrahedron L ett., 4$ (1961); A. Kotz and W. Zornig, J. Prakt. Chem., [2] (1906); A. P. Kfapcho, J. Org. Chem., 2%^ 2375 (1962); T. D. J. D 'silva and H. J. Ringold, Tetrahedron Lett., 4487 (1965).

the follOT-ring equations:

XgCH RCH(C02R ') 2 + CHX3 + NaOR* C(C02R)! X = F, Cl, Br R

-HX •h C K X 3 -1- NaOR

CHX

32 33 Ethoxycaxbonylcarbene and difluorcarbene are known to react

(32) D. L. Storm and T. A. Spencer, Tetrahedron Lett., I865 (1967); S. T. Murayama and T. A. Spencer, ibid., 4479 (19^9).

(33) P. Hodge, J. A. Edwards, and J. H. Pried, Tetrahedron L ett., 5175 ( 1966).

with o- met hoxymethyle ne ketones by 1,4-addition. Elimination of methanol

(whenever possible) yielded furans. 25

.CHOCH. N, -HOMe -> 0

Vinyl Azldes

Vinyl azid.es have been prepared in a number of ways. The simplest 34 one, azidoethylene, was prepared as early as 1910. Triazoethyl alco-

(5U) M. 0. Forster and S. H. TJe-vmian, J. Chem. Soc., gT, 2570 (19IO).

hoi was used as the starting material. After treatment with phosphorous tribromide halogen exchange was affected with sodium iodide and the re­ sulting 2-iodo-1-azidoethane was dehalogenated in the presence of alcoholic potassium hydroxide to give vinyl azide.

HOCH2CH2W3 BrCH2CH2% ICH2CH2W3 > CÏÏ2 = C H -N 3

3 5 a-Azidostyrene ivas prepared in I96I by the reaction of styrene di-

(55) 0. Smolinslîy, J. Amer. Chem. Soc., 8^ 448$ (1961).

bromide with sodium azide in dimethylformamide, followed by treatment of the bromoazide formed with potassium t-butoxide. In the subsequent year 2 6

Ph-CH-CHg > PhCH-CHaBr || I I DMF I C ^ Br Br N3 Ph N3

36 a more general method for the preparation of vinyl azides vas developed.

(56) G. Smolinsky, J. Org. Chem., gT, 555T (1962),

Some o f th e r e s u l t s a re shcnm h e lo v :

CH2 -X CH2 - X CII2

^ ^

R = CeHs o r O-CH3C3R4 ) th e n X = Y = Br

R = nC^lIs , then X = Cl, Y = OTs

Vinyl azides have also been prepared from p-iodo azides generated 3 7 by the addition of iodoazide to olefins. The addition of iodoazide to

(5T) a. Hassner, F. W. Foi'/ler, and L. A. Lei/y, J. Amer. Chem. Soc., 89, 2077 (1967); A. Hassner and F. ¥. Fcnrler, J. Org. Chem., 33, 2680 (1968).

R H I

RCH = CH2 — > ^ C ------C c ^ t -BuO®lP R -C = C H 2 / / . % H H % 27 olefins was highly stereospecific. Terminal olefins formed adducts where the azido function was at the 2-position. This is by far the most general method in preparing vinyl azides to date. However, ter­ minal vinyl azides cannot be prepared by this route. The only excep­ tion is the follc^fing case.

IN3, (®3)3C H ,C = CH2 > CH-CH2N3 ^C = C: I H''

80^

Other reported preparations of terminal vinyl azides are illustra­ s a , 39 ted by the equations belovr.

(38) J. H. Boyer, ¥. E. Kruegger, and G. J. Mikol, J. Amer. Chem. Soc., ^ 3504 (1967).

(39) G. Smolinsky and C. Pryde, J. Org. Chem., 2411 (1968).

a . 0 CH2W3 CH2N3

Ph-C-aigHg . PhCIiOH > PhCH-Cl

- 25° _ t - B u ( A ^ Cl I 1795 PhC = CIl2 + PhCH-CHNs 44% 2 8

Na% b . Y ie ld n o t DI# r e p o r te d

Br

OII 1. MeSOgCl R i ^ l 2, DMP/pyrldine ^ Ri NaNs ^ ■CEs C = CH-N3 Rg /

R i = P h, Rg = C I I 3 25^

Ri = Ph, Rg = Ph 50^

Vinyl Thiocyanates

Vinyl thiocyanate vas prepared hy the dehalogenation of the p-hromo 40 or p-chloro ethyl thiocyanates vith tertiary amines.

(40) J . C. H. E\m, J. Amer. Chem. Soc., ^ $Go4 (l959); J. C. H. Hva, U. S. Pat. 3,010,947; June 1, 1955; Chem. Ahstr., 4671e (1962),

XCHgCHgSCN + B CHg = CH-SCR + B-HX

X = Br, B = EtsN 80^ X = 01, B = PhCHgW( 0113)2 30^ 29 41 Tobler and Foster reported that vinylmercurie acetate reacted

(4l) E. Tohler and D. Foster, Z. Naturforsh, I36 (1962).

vith sodium thiocyanate to yield vinylmercuric thiocyanate. Thermal de­

composition of vinylmercuric thiocyanate at 100-120° and 100 ram gave a mixture vhich consisted of ^0% of vinyl isothiocyanate and 66/5 of vinyl thiocyanate hy vapor phase chromatographic anaJ-ysis. The actual yields of these two vinyl compounds were not reported.

CHa = CH - HgOAc + NaS CN CH2=CH-HgSCN

decomposition 100-120° /l00 mm

30^ CH2 = CH-N = C=S + CH2=CH-S-CHN 66^

Dialhyl Vinylphosphonates

The preparation of dialkyl vinylphosphonates is illustrated hy the following methods.

42 1. Vinylphosphonic dichlorides with alcohols.

(42) Ye L. Gerter, ^^Organophosphorous Monomers and Polymers, Pergamon Press, Inc., The Macmillan Co., New York (1962) pp 26-27 and references therein.

Org. h a se CH2=CH-P0(C1)2 + ROH CH2 = CH-P0(0R)2 30

One of the main methods of preparing the starting acid chlorides was to add phosphorous pentachloride to olefins, foUovred hy the treat- 43 ment of the adducts vith sulfur dioxide or phosphorous pentoxide.

(43) W. H. Woodstock, U. S. Pat. 24T14T2; Chem. A hstr., 4^, 7499 (1949).

RCH = CIÎ2 + 2 PCI. RCIIClCHaPCl4-PCl5

3 RCH = CIlP0Cl2 + 3 POCI3 6 SO; + 6 SOCI2 + 3 HCl

3 RCHClCHaPCki-PCls

2 P2 O5 3 R C îi=cirpoci2 + T POCI3 + 3 HCl

44 2. Alkenyltetrachlorophosphoranes -v/ith alcohols.

(44) G. M. Kosolapoff, U. S. Pat. 2389376; Chem. Ahstr., 40, 1336 (1 9 4 6 ).

R 'P C l4 + 3 ROH R'PO(OR)g + RCl + 3 HCl

•fdiere R’ is an unsaturated radical 31

5. Dehydrohalogenation of esters of p-halogenoalkylphosphonic acids, dehalogenation of esters of dihalogenoall^ylphosphonic acids, and dehy- 42 drat ion of esters of Qf-hydroxyalkylphosphonic acids according to the following general scheme:

R’CHX—Cl” 'R” ’P0(0R)2 -HX(R"X or HgO) ^ R»CH = GR"’PO(OR)2

where X = halogen or hydrogen R '' = halogen, hydroxyl or hydrogen

4. Base-catalyzed condensations of methylenehisphosphonate with aide- 45 hydes or ketones.

(45) D. Y. Wysocki, Biss. Ahstr., B 28 (4), l43T (196?)•

0 0 0 0 EtO^ f t^ O E t II EtO. t P -C H 2 - P . + C —- > P -C H = CRiR2 EtO '^ OEt R i^ R2 EtO

Rx = II, alley 1 or aryl R2 = alleyl or aryl 46 5. Arbusov type rearrangement.

(46) P. Tavs and H. Weitkamp, Tetrahedron, 26, 5529 (l9T0),

CH2 =CHC1 4- P(OEk)a CIl2 = CH-P0(0Et)2 + EtCl 190° DISCUSSION OF RESULTS

The first part of the present w rk is concerned vith the study of the stereoselectivity of an unsymmetrical carhene or unsaturated vinyl cation derived from the alkaline decomposition of ^-methyl-^-t-hutyl-

5-nitroso-2-oxazolidone. The second part deals i-rith the reactions of

N-nitroso-4^5^5“trimethyl-2-oxazolidone^ a conpound which cannot give an unsaturated carhene intermediate during the course of its alkaline decomposition. In the third part decomposition of l-(N-nitrosoacetyl- aminomethyl)cyclohexanol, was conducted in the presence of carhonyl compounds, nucleophiles, phosphorous compounds, and amines respectively.

The miscellaneous section includes the attempted nitrosations of 2- acctylamino-$-methyl-2-hutanol and ethyl N-(2-chloro-2-mathylpentyl)- carhamate; alkaline decomposition of $-nitroso-spiro[fluoren-9',^- oxazolidin]-2-one in the presence of cyclohexene; alkaline decomposition of methyl n-hutyl-N-chlorocarhamate, etc.

1. Preparation of 9-methyl-9-t-hutyl-N-nitroso-2-oxazolidone (j). 7 Compound (3) was prepared as described. The product of the Re- formatsky reaction between 3,3-dlmethyl-2-hutanone, ethyl bromoacetate, and activated zinc was treated with anhydrous hydrazine to give the acid hydrazide. The acid azide obtained from the nitrous acid treatment of the acid hydrazide was subjected to a Curtius rearrangement in refluxing

52 35 benzene to give 2-oxazolid.one. N-ITitrosooxazolidone 3 vas obtained from the nitrous acid treatment of 2-oxazolidone.

2. Decomposition of 3-methyl-3-t-butyl-N-nitroso-2-oxazolidone (5).

a. vith sodium methoxide in methanol

A solution of sodium methoxide in absolute methanol was added drop- wise to a stirred solution of the nitroso conçound in absolute methanol.

The evolved nitrogen %ms collected^ measured over water, and corrected 47 to standard conditions. After the usual ivork-up, products were iso-

(4 t ) See Generalization in the Experimental section.

lated by distillation. The trans and cis isomers were separated by pre­ parative vapor phase chromâtography.

The decomposition of (3) gave a mix’ture of methyl trans-2,3^3-tri- methy 1- 1-butenyl ether (^ ) and methyl cis-2,3;5-trim ethyl- 1-butenyl ether (^ ) in 82^ overall yield. By vpc analysis the trans and cis isomeric vinyl ethers were found to be in a ratio of 97:3-

I / CH3OH CIÎ3^ OCH3 CH3'' II CII2 -N -N O

(3 ) ( 3 6 ) t r a n s (3 7 ) C l£

(major) (minor) 34

The foUoîfing nmr signals vere oh served for 3^ and 37. The struc-

CÏÏ3O ^ C C = C. t

T (C C lt) / \ e t jc t

^ CH3 t-Bu 8.45 8.98

21 t-Bu CH3 8.89 8.52

tures of ^ and 21 ivere assigned according to the observation in rrnir 48 made hy Meyers and Sataty that the signals of the protons trans to

(48) C. Y, Meyers and J. Sataty, token from the Ph.D. Dissertation of J. Sataty, So. 111. University, Sept., 1970.

the heteroatom (O and S) across a carhon-carhon double bond are shifted

upfield more than are those from the cis protons.

The decomposition of other 3“nitroso-2-oxazolidones with sodium

5 methoxide in the presence of absolute methanol has been reported. The

formation of vinyl ethers could be explained by the unsaturated car­ bene insertions into the O-H bond or by the reaction of a vinyl cation with alcohols. In the present experiment if an unsaturated carbene

intermediate is assumed, its insertion into the O-H bond w ill favor the formation of 2§ over 2 [ ty virtue of the attack on the alcohol from the less hindered side of the carbene. 55 49 According to the calculations hy Gleiter and Hoffman singlet

(49) R. Gleiter and R. Hoffman, J. Amer. Chem. Soc., ^0, 9457 (1968).

carhenes at an unsaturated carhon are preferred to triplet. If IT is

assumed to he a singlet carhene, it m il approach methanol m th its

vacant orhital in the plane of the paper. Clearly, the side m th the t-hutyl group is more hindered. The formation of ^ is therefore

fa v o re d .

(CH3)3C 0 (CH3)3C^ q (CH3)sC ^ ^H 0 = 0: > 0=CT ^ ^ 0=0, OH3 ^ CH3 ^ 0 ^ OH3 OOH3 H ^ OH3

( 1 7 ) H"^” OH3 (36)

If a vinyl cation is assumed to he the intermediate, isomer $6

TTOuld s till he predicted to he the major product.

A priori a vinyl cation can have two structures: a linear struc­ ture ^ with a sp-hyhi’idized carhon and an empty p-orhital, or a tri- gonal structure 39 with a sp -hybridized carhon and an empty sp^-orhital.

, Q Q / 9 / o 0 — R ''0--- 0 ^

ô h " T 0 %

( 3 8 ) (39) 56

Based on the analyses of the relationship of the substituents in the reactants and the products in the recent solvolytic studies of vinyl 50 cations the linear sp-hyhridized geometry ^ is the preferred one.

(50) For a complete review of the structure of vinyl cations see the chapter of vinyl and allenyl cations hy Peter J. Stang in ''Pro­ gress in Physical Organic Chemistry,'' 10 (l9T2), in press.

Thus, hy assuming that the geometry of vinyl cation W is linear

With its vacant p-orhital in the plane of the paper the approach of the methanol molecule w ill he mainly from the less hindered side to give

36 as the major product.

(0113)30^ V (CH3 ) 3 C s _JJ© (CH3 ) 3 C \ / H C = C -H ----- > 0=0 > 0 = 0^ O I I 3 A 0 H 3 ^ (^0% OHa^ OOH3

U C I I 3 (40)

. . q . ( M ) H ' " OH3

In summary, the decomposition of 3 in methanol gave ^ as the major product and 37 the minor product. This stereoselectivity can he ex­ plained in terms of an unsaturated carhene 17 or a vinyl cation 40 inter­ m e d ia te.

In the case where the size of the substituents at the (3 carhon of the unsaturated carhene or vinyl cation does not vary as greatly as in the present case, a more even distribution of the trans and cis products 51 has heen reported. 57

(5l) M. S. Nmrman and S. Gromelski, taken from the Ph.D. Dissertation of S. Gromelski^ Ohio State University, 1971.

A.

Q, CH2-N -N O

48^ 52^

h. with sodium phcnoxide in phenol-glyme

A solution of 9- methyl-9-t-hutyl-9-nitroso-2-oxaz olidone (3) in glyme vas added dropvise to a stirred solution of sodium phenoxide and phenol in glyme. The theoretical amount of nitrogen vas evolved in I8 hr. After the usual vork-up, the mixture vas distilled and the isolation of the products vas carried out hy preparative vpc.

The products obtained from the decomposition of ^ vith sodium phen­ oxide in phenol-glyme are shovn in Table 5-

The structure of 2-methoxyethyl trans-2, 2 , 3-trimethyl-1-butenyl ether

(4l) vas established by the elemental analysis, ir, nmr, and mass spec­ tral data. The assignment of the trans stereochemistry vas based on the comparison of nmr T values of the t-butyl and the methyl groups vith methyl trans-2,3,3 -1 r imethyl- 1-but enyl ether (^ ). The former has pro­ ton signals at t 8.97 for the t-butyl group and t 8.45 for the methyl group, vhile the latter has signals at T 8.98 for the t-butyl group and

T 8.45 for the methyl group. $8

T able 5

Allîaline decomposition of ^-methyl-5-t-bntyl-^-nitroso-2-oxazolidone (5)

■with sodium phenoxide in phenol-glym e

( 053)3 0 \ 0 0 PhONa O E s^ 1 \ ------^ P ro d u cts 1 ^ 0 - 0 PhOH 4. CH3OCII2 CH2OCH3 CH2 — N—NO (5)

P ro d u c ts % Y ie ld

(hi) ( 0113)30 = 00113 7 .7

PhOOH3 52. 7^

(OH3 )sO ^ H (41) 0 —0 4 5 .7 0H3 ' ' OCII20H2O0H3

( 053)3 0 ^ (42) 0= 0H (0P h) 2 .2 Oils'"

( 0H3 )3C ^ ^CHgOPh ( ^ ) 0 1 1 .5 II OH2

(OH3)sO.^ 0 0 ^ 4 .8 ™ 3 " \ = o / m a. based on one mole of anisole per mole of ^-nitroso-2-oxazolidone u sed. 39

The stereochemistry of the very small amount (2.2^) of phenyl

2,3, ^-trimethyl-l-hutenyl ether (^ ) vas difficult to determine. Due to the phenyl group adjacent to the oxygen atom the t-hutyl and the methyl proton signals have been deshielded too far dounfield for any m ean in g fu l com parison T-rith e ith e r ^ o r 3 7 .

2; 2-Dimethyl-3-pentyne (]0) could conceivably come from a carbon skeleton rearraaigement.

(CH3)3C. © e /E ^ C = C - H ------> C H 3 C = C ^ > CII3C = 0-0(0113)3 CH3^ 0 ( 0113)3

(4 0 ) (43)

In a similar study the cleavage of glyme vas reported in the decom- 4 position of 5^5“dimethyl-3-nitroso-2-oxazolidone (4). Thus, the com­ plexation of the vinyl cation W vith glyme takes place from the less hindered side to form an oxonium salt Displacement of ^ by the phenoxide ion gives anisole and the vinyl ether 4l.

(CH3)3C. © (053)30. Phcp 0 = 0-11 > 0 = 0 PhOOH3

0 5 3 ^ 053-^ 0 . OH^ ^05205200113 (40) / O ^ ( ^ ) 0H3 ' 'OH2OH2OOH3

(053)30. ^5 4- 0 = 0 ^ 053 OO52OH2OOII3

(41) ko

An intermediate other than ^ must he invoked in order to ex­ plain the formation of 2-phenoxymethyl 3^3-dimethyl-1-hutene (4$). In their attempt to prepare pure 2-methyl-1-propenyl phenyl ether (46) 4 Newman and Beard reported the presence of another product; 2-methallyl phenyl ether (4t). Mechanisms which involve 1,3-hydride shifts were discussed. Based on the results from the deuterium experiments one or more than one of the following mechanisms were Believed to he involved in the formation of 4?.

Mechanism (l)

CHs. © CNs. phfP CHs C = C-H ------> 7 c -CH2------— ^ --- > ^C-CHg-OPh CHa'' CHs ^

(8 ) ( ^ )

PhcP

C = C ^ CHa^ OPh

(46)

Mechanism (2)

CHa^ H CHg ^ -Ng 4 l

Mechanism (3)

© CH3 ^C-CH = N2 < .... Ph(T£> H-CH2' H

OPh C-CH2-N2^ — 47 CH2^ -N2

Similarly the above mechanistic pathways can also be applied to

account for the formation of ^ in the present experiment.

3. Preparation of N-nitroso-4,5;5-trimethyl-2-oxazolidone (48).

Compound ^ was prepared by the reactions outlined in Scheme VII.

A Reformatsky reaction was carried out on acetone, ethyl cy-bromopr op don­

ate and zinc to give the hydroxy ester Treatment of the hydroxy

ester with anhydrous hydrazine led to the acid hydride The azide

obtained from the nitrous acid treatment of the acid hydrazide was con­

verted to the 2-oxazolidone ^ by a Curtius rearrangement. Nitrosation

of the 2-oxazolidone with nitrous acid yielded N-nitroso-2-oxazolidone

W.

CompouTid W was chosen for study because in accordance with the

suggested mechanism (see Scheme IV) its decomposition could not concei­

vably proceed via a unsaturated carbene intermediate. An alternative mechanism would be through a vinyl cation intermediate. k2

Scheme V II

0 0 CHa^ ^OH II II 1 . Zn + CH3CH C OEij 2 HCl CHs^ CHs CHa'^ CH OEt Br I CHa

(4 9 ) ( t4^ )

NH2HH2

0 0 CHa^ , 0 H II CHa .OH II HONO

CHa CH Na 5 ° CHa CH^ HE- m 2 I I CHa CHa

( ^ ) {63%)

-Ng

CHa CHa^ -0 C 0 / N HONG CHa C= 0 0=0 / CH— m 0H - ¥ ^ CHa' CHa NO

( 51) ( 83^ ) (4 8 ) (9 3 ^ ) ^3

0 II © CE3^ O-C-OB CEs^ CEs^ © C. ^ > ^C = C_ z_ ^ ^ C = C -C E 3 CHa^ CE-Mg^ -EOC-OR CE3 CE3 CEs'^ 0 C B 3

4. Decomposition of N-nitroso-4,5>5-trimethyl-2-oxazolidone (48).

a. in 2-metho>yethanol containing sodium iodide.

A 20% solution of sodium 2-methoxyethoxide in 2-methoxyethanol vas added to a solution of N-nitroso-2-oxazolidone ^ in 2-methoxyethanol saturated vith sodium iodide. After the evolution of the theoretical amount of nitrogen, the mixture vas vorked up as usual and distilled.

By vpc analysis of the products 8.2% 3-methyl-2-butanone ( ^ ) , 7.1% 2- methoxyethyl 3“i'iethyl-2“'butenyl ether (53); and 22.4% 2-methoxyethyl

3-methyl-l-huten-3-yl carbonate (^ ) (see Table 4) vere shcnm to be present. Many other minor components vhich vere not identified vere also noted. Surprisingly, the expected 2-iodo-3-methyl-2-butene (55) vas not among the major components.

By postulating that a vinyl cation is involved, the formation of

52 and ^ can be rationalized (Scheme VIIl). Vinyl cation ^ can react either vith the 2-methoxyethoxide ion to form ^ or vith the hydroxide ion to form In viev of the absence of the vinyl iodide ^ vinyl c a tio n ^ appears to shov a preference for the reactions vith the 2- methoxyethoxide ion or the hydroxide ion rather than the iodide ion, a

3 fact contrary to that observed by Nev/man and Beard. T able 4

Alkaline decompositions of N -nitroso-4,5^ 5”’trimethyl-2-oxazolidone (48)

CH a^ C 0 B ase C =0 P ro d u c ts CH — N -NO CHa"

(48)

P ro d u c ts % Y ie ld

A. from B. from C. from CHaOCHaCHsOWa PhOWa CHaOCîIaCIIaONa + N al + PhOH + CHaOCHaCHaOH + CH3 CCH2 CH2 OH + glyme

0 CHa^ II CH - C - CHa 8.2 CHa^

( 52)

CHa . O x ^ C H a^ c = c , CHa OCHa 7 .1 2.6 9 .6 CHa CHa

(53) 0 II CHa ^ ^ 0 - C - OCHaCHaOCHa 22.4 1 9 .8 CHa^ '"CH-CHa

(54)

PhOCHa 3 .9

CHa^ ^CHa c = c ( ^ 10.6 CHa^ OPh (6 0 ) 45

Scheme VIII

CHs^ CHr C 0 © > — 0 . 0? OCHp CHpOCHc' 0H3' ' I \ = 0 CHs X ^OCHgCHgOCHs CH — N-NO ^C H — N ^ _ CHs' CH. N = QV' (48)

0 0 II CHs . - C - OCHgCHgOCHs g % ° ^ " OCHaCHgOCHs ^ HOOHgCTIsOCHs 0 ^C CHs^ \ ^ -ScHsCHgOCHs CH s^ \ © C H -N = N -O H / C H -N = N -0 Oh s '" CHs © -OH

0 II CHs ^ / 3 r C - OCHgCHgOCHs © CHs^ ^N s® OCHgCHgOCHs C = C % ^ CHs'" CHs

H V CHs (59)

(57) -Np

CHs^^^^^O-CH,CH,OCHs CHs. © C =C -C H s CHs^ ^CHs CHs

( 55) ( 56) © ©OH

0 CHs ^ II CHs. .OH CH-C C = C^ \ CHs^ CHs C H s^ CHs CHs CHs

( 52) ( 55) 46

Assuming ^ loses nitrogen to give the carhonium ion ^ instead of

proceeding to give vinyl cation the subsequent loss of a proton

from 58 leads to the carbonate 54.

0 0

CHs 0 - C - OCH2CH2OCH3 CHs 0 - C - OCH2CH2OCHS

/ \ ® CHs C -C H 2 / ^1 CHs H H (57) ( 58)

0

CHs 0 - C - OCH2CH2OCHS c CHs^ '^CH^CHs

( 54)

Compound ^ was the major product in this reaction. If the above

assuiiption ivas correct, it might imply that the loss of nitrogen from

to was more facile than the elimination reaction from 57 to 59

as sho-vm in Scheme VIII. One can perhaps rationalize that the methyl

group next to the carbonium site of may have a stabilizing effect on the ion, thus providing a driving force for the loss of nitrogen.

b. in phenol-glyme.

A solution of $-nitroso-2-oxazolidone ^ in glyme was added to a

solution of sodium phenoxide and phenol in glyme. The total phenol to

glyme ratio was (l:l)m . The theoretical amount of nitrogen was collected h i

in 2 hr. After the usual work-up and distillation vpc analysis of the products shotred many components^ hut only three were identified, 2.6%

2-methoxyethyl $-methyl-2-hutenyl ether 3-9^ anisole, and 10.6% phenyl $ -methyl- 2-hut enyl ether (^ ) (see Tahle h).

In comparison with the decomposition of 3,3-dimethyl-3-nitroso-2- oxazolidone (h) under similar cond.itions the degree of the cleavage of glyme was much less in this experiment, and compound 60, a product presumably derived from the reaction of vinyl cation ^ with the phen­ oxide ion, became the major product of those isolated.

c. in 2-methoxyethanol.

A 20% solution of sodium 2-methoxyethoxide in 2-methoxyethanol iras added to a solution of 3-nitroso-2-oxazolidone ^ in 2-methoxyethanol.

The theoretical amount of nitrogen "VTcis evolved in 0.5 hr. By suitable work-up and preparative vpc 9.6% of 2-methoxyethyl 3-methyl-2-butenyl ether (_^) and 19.8% of 2-methoxyethyl 3-methyl-l-buten-3-yl carbonate

(5^) were isolated (see Table 4).

The yield of the vinyl ether ^ was lovrcr than that of the carbon­ ate _54. This may imply that the formation of cation ^ is preferred rather than the vinyl cation On the other hand, the total yield of the products in this reaction was quite lo\r and not all of the compo­ nents shovm in vpc were isolated and identified. The possibility remains that there might be other products which could be derived from the vinyl cation but were in such small amount or so volatile that their isolation became very difficult. For example, 1,1-dimethyl allene, a product which 48 could presumably be formed by the loss of a proton from the vinyl ca­ tion ^6, might have been present but eluded detection because of its high volatility.

5. Preparation of l-(N-nitrosoacetylaminomethyl)cyclohexanol (61).

Compound ^ was prepared according to the method previously repor­ t s ted. A modification was made in the nitrosation step in which methyl­ ene chloride was used as a co-solvent (15 ml per 50 ml of acetic acid used). The use of methylene chloride kept the acetic acid solution of the amide from freezing at ice temperature during the reaction without sacrificing the yield of the product.

Compound 6l \ras chosen for study because the alkaline decomposition 22 of this compound in the presence of a phase transfer agent was con- 23 sidered to be a superior method of generating the unsaturated carbene.

6. Decomposition of 1-(N-nitrosoacetylaminomethy 1 )cyclohexanol (^ ) in the presence of ketones.

The sodium hydroxide solution was added dropwise to a stirred solu- 22 tion of nitrosoamide 61, Aliquat $$6, and the corresponding ketone in pentane held at -10 to 10°. The evolved gas was collected and measured over water. After the usual work-up the mixture was distilled and the isolation of the pure products was carried out by preparative vpc.

The yield of the divinyl ethers from the corresponding ketones are shown in Table 5- The divinyl ethers were identified by their elemental analyses, nmr, ir, and mass spectra. Where accurate elemental analysis

(w ith in O.yfj) could not be obtained due to the instability of the com- 49

T able 5

Alkaline decomposition of 1-(ll-nitrosoacetylaminomethyl)cyclohexanol (6l) in the presence of ketones and aldehydes 0 OH R i P ro d u cts o < : C% 5055 WaOH Aliquat 536 (6 1 )

Rx Rs P ro d u c ts^ % Y ield

h CHOI3 E t E t 22

C%CH3

O I3 C -CH 3 (0113)201 (013)201 4 .4 G — C ^ 0 1 - 0 1 3 CH3

- ( CII2 ) 5“ 52

^ OI3 ( 013)30 H 4 .5 C - C — O I3 il 1 G O I3

( 0 1 3 ) 2 0 1 H 35.T O C . c - Il CH3 G a. The products listed here were not the only products isolated in these reactions. h. Wmr shovred a mixture of els and trans isomers. 50

pound or the contamination "by im purities, the exact mass measurement

was also used. Divinyl ethers were also treated with dilute hydro­

chloric acid and the resultant mixtures of cyclohexanecarboxaldehyde and

the corresponding ketones were compared with the authentic samples in

nmr, vpc retention times, and the molecular weight (by mass spec) of

their 2,4-dinitrophenylhydrazine derivatives.

Products other than the divinyl ethers isolated from these reac­

tions were acetoxymethylenecyclohexane (§2) (lO-15^), cyclohexanone

(approx. 5% from the reaction of diethyl ketone or diisopropyl ketone),

cyclohexanecarboxaldehyde (approx. 5^), and cycloheptanone (approx. 5^)-

By assuming a mechanism sim ilar to those proposed for the decom- 1,5 position of N-nitroso-2-oxazolidones which involves either a vinyl

cation or an unsaturated carbene intermediate the formation of the pro­

ducts fi’om the decomposition of ^ can be accounted for (see Scheme IX).

The base promoted elimination of water from the diazonium ion 65

g iv es 6k, which loses nitrogen to form the vinyl cation 6^ or loses a proton first, followed by the loss of nitrogen to form the unsaturated

carbene 66.

An alternative mechanism which can lead to the vinyl cation ^ or the unsaturated carbene 66 is shoï-m in Scheme X. The hydroxy lie proton

is removed by the base in the first step. The attack of the anion at the carbonyl function gives a cyclic intermediate which eventually leads to the diazonium ion The subsequent conversion of 6k to 65 or 66

is the same as in Scheme IX. 51

Scheme IX

OH CHa HO' 'CHa

(61 ) 0 If -HOCCHa

OH OH HgO ,0 N= N-OH N—N -O

0 -OH

-HgO OH 0 /H -Na © -OH = C -H CX ^ © Ng

0 OH (A) ( 6 5 ) (65)

© -H

-Ng C=Na ------

(66) Scheme X

CHs 0 CHs II Ou —u -C -C— uns H s 0 - C - ^ ® O\ H = H - 0~

© H

0 0 11 .H; © / i^p - C - CHs © O -C -C H s 0 ,OH -OH H -HgO T c - H ^ N =N -O H ©S / \ H H (64) -OCCHs HO

vn ro 55

If the vmsaturated carbene ^ reacts •with the oxygen atom of a ke­ tone to give a l,3“dipolar intermediate as hypothesized in the cases of the copper catalyzed decomposition of ethyl diazoacetate in various ke- 26,27,28 tones reported in the literature, a proton shift of an a- hydrogen or protonation of the dipolar species 6j_, followed by the for­ mation of a double bond leads to the divinyl ethers.

" s . 0 I

+ R1-C-OHR2R3 V V ° ' ' 0 - 0 ^ R i

^ (6T) (68)

o \ R i

Another possible mechanism is by going through an allene oxide intermediate as shoim below. Hovrever, there has been no precedent for such allene oxide rearrangements reported in the literature.

Since the enolization of ketones is base catalyzed, the unsaturated carbene 66 can presumably insert into the 0-H bond of the enol forms 5^

0 0 / \ / R i iP Shih i f t ^ 68 ^ ^ = C : + R1-C-CHR2R3 ^ ^^C R sR s (66 )

Ri C' c © II CR2R3 or react with the enolate ions, foU.oimd hy protonation to give the divinyl ethers 68.

OH Ri I R i — C = CR2R3 © \ C: — CR2R3 > 0 H ^ © (66)

© 0

Ri -C=CR2R3

Ri E l I p X » \ c " ^ ^ C — CR2R3 c ^C -C R gR g 0 O' (68) 55

Alternatively, the vinyl cation 6 ^ can also lead to divinyl ethers

hy reaction with an enolate ion or with the enol form of the ketones,

followed hy deprotonation.

The formation of acetoxymethylenecyclohexane (62) can he visualized hy the reaction of either the vinyl cation ^ or the unsaturated car- h ene 66 with the acetate ion derived from the cleavage of the carhonyl-

nitrogen hond of 6l (see Scheme IX and X).

0 0 / H II © II C-H + O -C -C H 3 0 CHs

(62)

0 0 II II C: + 0 -C -C H c © C \ C -C H s

(66 )

The reaction of ^ with water gives cyclohexanecarboxaldehyde, one

of the product isolated.

The diazonium ion 6 ^ can lead to cycloheptanone hy the follovring pathvray.

0

OH “OH -N; ©

( 6 5 ) 56

7. Decomposition of l-(N-nitrosoacetylaminomethyl)cyclohexanol (^ ) in the presence of aldehydes.

A 50^ sodium hydroxide solution vas added dropvise to a solution of the nitrosoamide Aliquat 3^6 and the corresponding aldehyde in pentane, held at -5 to -15°. The evolution of nitrogen vas quantita­ t i v e in 0.25 t o 0.5 hr. After the usual vork-up the mixture vas dis­ tilled and the isolation of the products vas carried out by preparative vpc.

The yields of the of,g-unsaturated ketones are shovn in Table 5-

The conjugated ketones vere identified by their elemental analyses, nmr, ir, uv, and mass spectra. The 2,4-dinitrophenylhydrazine deriva­ tives vere also prepared. Furthermore, cyclohexylidenemethyl t-butyl ketone (69) vas prepared by an independent route for comparison (see

Scheme XI).

Triethyl phosphonoacetate vas prepared from the reaction betveen 52 triethyl phosphite and ethyl bromoacetate. The sodium salt of tri­ ethyl phosphonoacetate obtained from the reaction vith sodium hydride 53 vas treated vith cyclohexanone to yield ethyl cyclohexylideneacetate,

( 52) J . Wolinslty and K. L. E rick so n , J. Org. Chem. , 3 0 , 2208 ( 1965).

(5 3 ) Org. S y n ., p 44 (1965).

vhich vas then saponified to give cyclohexylideneacetic acid. Treatment of the conjugated acid vith t-butyllithium gave cyclohexylideneraethyl t-butyl ketone (69). 57

Scheme XI

0 165- 170° E tO ^ t ( E tO ) ^ + BrCHgCOsEt ^P-CHgCOgEb -E tB r EtO

(75^)

NaH

0 EtO^ t © H © P - CHCOgEb Na O' COaEt E tc

( 67^ )

1. NaOH 2. HCl

CHs ^ 0 CH3-O8 L i^ I .H CHs H CHs / I C C — CHs ^-----' COgH II I 0 CHs

(86^) (69) (47^) 58

The formation of the cv, p-iinsatixrated ketones can he explained hy a

direct unsaturated carhene 66 insertion into the carhonyl-hydrogen hond

of the corresponding aldehydes. In support of this hypothesis an ex­

periment using a deuterated aldehyde should he run in the future. If

the insertion does talce place one should he ah le to find the incorpora­

tion of deuterium at the carhon next to the carhonyl function.

C:'-...... --C—R ^ ^R

Interestingly, in the alkaline decomposition of ^ in the presence

of isohutyraldehyde no divinyl ether "was isolated although the molecule possesses an enolizahle hydrogen.

The yield of the a, (3-unsaturated ketone vas very low vhen 2,2-

dimethyl propanal vas used. This might he due to the steric hindrance

of the t-hutyl group vliich inhibited the unsaturated carhene insertion.

In a separate experiment in "v/hich the nitrosoamide ^ iras decom­

posed in isohutyraldehyde vith trlethylamine as hase, there vere isolated

15% of acetoxymethylenecyclohexane (62) and only 12.6% of cyclohexyli-

denemethyl isopropyl ketone. Thus, the choice of an organic hase (tri-

ethylamine) did not improve the yield of the a,P-unsaturated ketone. 59

8. Decomposition of l-(N-nitrosoacetylatninomethyl)cyclohexanol (^ ) in the presence of nucleophiles.

a. sodium azide.

A solution of the nitrosoamide 6 l in pentane vas added drop'vrise to a stirred mixture of sodium azide^ sodium hydroxide, Aliquat 55^, and vater at The evolution of nitrogen iras quantitative in 15 min.

After the usual vork-up the crude vinyl azide vas purified hy passing through neutral Woelm alumina oxide activity grade I vith hexane. The yield of the azido-methylenecyclohexane vas (see Table 6). The vinyl azide \ras identified hy its elemental analysis, nmr, and ir spec­ t r a .

h. potassium thio(%'^anate.

A solution of the nitrosoamide 6 l in pentane \m s added dropvise to a stirred mixture of potassium thiocyanate, sodium hydroxide, Aliquat

336, and vater, held at 5-7°• After the theoretical amount of nitrogen had heen collected (in 15 min), the aqueous layer of the mixture vas ex­ tracted vi.th ether and the combined organic phase vas vorked up as usual. After distillation cyclohexylidenemethyl thiocyanate vas obtained

in 39^ yield (see Table 6). The vinyl thiocyanate vas identified hy elemental analysis, nmr, and ir spectra.

c. sodium iodide.

A solution of the nitrosoamide 6 l in pentane vas added dropvise to a stirred mixture of sodium iodide, sodium hydroxide, Aliquat 35^, and vater, held at 3-5°. The theoretical amount of nitrogen \ras evolved in 60

T able 6

Alkaline decomposition of l-(K-nitrosoacetylaminomethyl)cyclohexanol

(61) in the presence of nucleophiles

OH NO / I Nucleophiles _ M pu > P ro d u cts

C H ^ HaOH a J Aliquat 356 ( 61 )

Nucleophiles Products % Y ie ld

NaNg 56

KBCN 59 o c . . .

Nal 72 o ^ : 61

25 min. After the usual work-up distillation gave 72^ of iodomethyl- enecyclohexane (see Table 6). The vinyl iodide was identified hy com- 3 parisen of its ir and nmr spectra with those of an authentic sample.

The products listed in Tahle 6 can he explained hy either the reaction of the vinyl cation ^ with the nucleophiles or the reaction of the unsaturated carhene 66 with the nucleophiles, followed hy pro­ tonation of the ions derived therefrom. 35-37 Most of the methods available for the preparation of vinyl asides

(see H istorical section) give only products with the azido function at the more substituted carhon of the double hond. The present route pro­ vides a general method for the preparation of terminal vinyl azides.

Very few methods for the preparation of vinyl thiocyanates have 40,41 heen reported in the literature (see Historical section). In view of the potential application of this class of compounds as monomers for polymerization, the present route offers a valuable new synthetic method for substituted vinyl thiocyanates.

9. Decomposition of 1-(H-nitrosoacetylamlnomethyl)cyclohexanol (6l) in the presence of triethyl phosphite and acetone.

Carhenes are known to react with triphenyl phosphine to form 54 ylides. The study of the present reaction was undertaken to see if

(5 ^) G. W ittig and M. Schlosser, Ange;/. Chem., 7^ 524 (196O); D. Sey- ferth, S. 0. Grim, and T. 0. Read, J. Amer. Chem. Soc., I5IO (i960); ibid., 8 ^ 1617 (1961); D. Seyferth, J. K. Heeren, G. Singh, S. 0. Grim, and W. B. Hughes, J . Organometal. Chem., 267 ( 1966); A. J . S p e z ia le , G. J . Marco, and K. W. R a tts , J . Amer. Chem. S o c ., 82, 1260 ( 1960); A. J . Speziale and K. W. R a tts , J . Amer. Chem. S o c ., 854 (1962). 62

the vmsatiirated carhene 66 vould. yield an ylide vith triethyl phos­

phite. If such \Teve the case, further reaction of the ylide tâth ke­

tones could lead to aliénés.

A solution of nitrosoamide 6l and 1.1 eq of triethyl phosphite in

pentane at -10° vas treated vith sodium methoxide in portions. After

the evaluation of nitrogen ceased {72% in 1 hr) the solid in the mixture

vas filtered and the filtrate vas concentrated. Acetone vas added to

the residue. After stirring for one hour distillation gave t\ro f r a c ­

tions vhich vere analyzed hy vpc. The products obtained are sho-v/n helovr.

1. NaOCHa, (EtO)aP OH jjo p en tan e > 2. CH3COCH3 0

(6 1 )

^ H 0 y P — OEt I OEt 26 .6% ( 7 0 )

The expected allene vas not detected.

Mechanisms "vAiich involve either the vinyl cation 63 or the unsatura­ ted carhene 66 can he postulated to explain the formation of cyclohexyli­ denemethyl diethyl phosphorate (jO). 63

0 OŒIa ^ ^=^-H + P(OEt)s V P —OEt -CHaOEt /\" (6 5 ) EtO OEt

,H 0 ( / P - O E t I OEt (70)

C: + P(0Et)3 > \ \___ ( I® EtO'^ 1 ^O Et OEt (66)

10. Decomposition of 1-(N-nitrosoacetylaminomethyl)cyclohexaxiol (^ ) in the presence of trialkyl phosphites.

Since the vinyl phosphonate 70 obtained, from the previous experiment

is a compound of interest, attention vas directed to the improvement of the yields of this kind of products.

a. cyclohexylidenemethyl dimethyl phosphonate.

A solution of equimolar amount of nitrosoamide ^ and trimethyl phosphite in pentane 'v/as treated at 5“T° 'vrith sodium methoxide in portions. 6h

After the nitrogen evolution (72% in 15 min) and the usual vork-up dis­ tillatio n of the residue afforded 10.8% of cyclohexylidenemethyl dimethyl phosphonate.

h. cyclohexylidenemethyl diethyl phosphonate (70).

A solution of 1 eq. of nitrosoamide ^ in pentane was added drop- wise to a stirred ice cold mixture of 5 eq. of triethyl phosphite, sodium hydroxide, Aliquat 5$6, and water. After the nitrogen evolution (72% in

15 min) and the usual work-up distillation of the residue yielded pro­ ducts which by vpc showed 5.6% cycloheptanone, 4.2% triethyl phosphate, and 42% cyclohexylidenemethyl diethyl phosphonate (70).

When a 50% solution of sodium hydroxide was added to a mixture of the nitrosoamide, triethyl phosphite, pentane, and Aliquat 536, follovred by the same work-up as above, the vinyl phosphonate 70 was obtained in

44.2% yield.

11. Decomposition of 1-(N-nitrosoacetylaminomethyl)cyclohexanol (6l) with pyrrolidine.

A stirred solution of a ten fold excess of pyrrolidine in hexane at

0° was treated dropirise with a solution of the nitrosoamide ^ in hexane.

After the nitrogen evolution ceased (89% in 0.5 hr) excess pyrrolidine and the solvent were removed on a rotary evaporator. The residue was distilled and the isolation of the products was carried out by prepara­ tive vpc. The products obtained are sha\m belovr.

N-acetyl pyrrolidine (7l) was identified by an independent synthesis from the reaction of pyrrolidine and acetic anhydride. N-(l-Hydroxj'- ‘ 65

n NO 'N ' 9. OH OH "" II I CHs ----- > N- C -CHs + hexane

(71) (72)

6k% 22$

cyclohexylmethyl)pyTrolidine (72) 'vra.s identified hy the elemental analy­

sis, nmr, ir, and mass spectra.

In order to account for the products a mechanism is proposed (see

Scheme XII). Assuming the attack of the pyrrolidine on ^ takes place at the carhonyl function cleavage of the C-N bond leads to the formation of N-acetyl pyrrolidine (T1)- Another molecule of pyrrolidine attacks the diazonium ion to give 72.

As pyrrolidine is not as strong a base as sodium hydroxide, the base promoted dehydration of the diazonium ion becomes more difficult.

This might be the reason why products derived from the vinyl cation 6 ^ or the unsaturated carbene 66_ were not detected in this reaction.

12. Miscellaneous. 9 a. Decomposition of 5-nitroso-l-oxa-5-azaspiro[4,5]decan-2-one (l2).

(l) in diethylamine.

Freshly distilled diethylamine in large excess amount was treated w ith J2 in portions. After the gas evolution ceased (in 9 min), distilla­ tion on a spinning-band column yielded 56.6^ cyclohexanecarboxaldehyde and a residue (22$ w of the starting nitroso compound). The product was identified by the comparison of its ir and nmr with those of an authen­ tic sample. 66

Scheme X II

c

0 OH j|±) / ----- \ pH II H N = N -O H <- = N - 0 ^ + C H 3 - C - N ©

© -OH

OH © C H 3 - C - N N: II 0

(71)

o

OH / " A / ® H - i P N N ©

(72) 67

The amount of gas evolved during the reaction vas 1.4 eq. How­ ever, no attempt \tels made to analyze the effluent gas.

(2) in the presence of cyclohexene and a phase transfer agent.

A 25^ solution of sodium hydroxide was added dropwise to a well stirred solution of 2^, cyclohexene, benzene, and Aliquat 336. The theoretical amount of nitrogen was collected in 4 hr. After the usual work-up, distillation yielded 43^ of bicyclo[4.1.0]hept-T-ylidenecyclo- 5 hexane (73).

(73)

17 b. Decomposition of 3-nitroso-spirorfluorene-9',5-oxazolidin]-2-one

(74) in the presence of cyclohexene.

A stirred solution of j4 and cyclohexene in benzene was treated with solid sodium ethoxide. The mixture was heated at 60-70° for 2 hr. After the evolution of the theoretical amount of gas (in 2 hr) and the usual work-up the residue 'vra.s chromatographed on silica gel. There were ob-" tained 12.7^ of 9-(bicyclo[4.1.0]hept-7-ylidene)fluorene (75) and 40.7% of fluorenone.

+ NaOEt benzene N-NO

(75) 68

c. Attempted nitrosation of 3-acetylamino-2-methyl-2-butanol (j6).

Compound 76 vas prepared according to the sequence of reactions as shovm belov.

OH CH3 , CH3^1 0 C \ KOH CH3' 0 = 0 CH3 '^ C H - M 2 / CH— KH C H 3 CH3' 0 0 ( 51) II II CH3 C-0 -C-CH3

C H 3 , OH H

C H 3 I II CII3 0

(76) 7395

All attenpts to nitrosate 76 failed to give a high conversion to the desired W-nitroso product. The N-nitroso compound iras desired as a vinyl cation precursor.

d. Attempted nitrosation of ethyl (H-2-chloro-2-methylpentyl)carbamate

(7 7 ). 55 Compound 77 vas prepared as shovn belov.

(55) T. A. Foglia and D. Svern, J. Org. Chem., 3^23 (1966). 69

0 0 II NaOAc - HOAc II Cl BtOC-M2 + 2 Clg EtOC-N Cl

CH3CH2CH2CH = CH2 I CHs

Cl 0 Cl 0 II Agueoi^s I II CH3CH2CH2C - CH2 - N - c - OEt CH3CH2CH2 -C-CH 2 -N -C - OEt NaHS 03 I I I 1 CH3 H CH3 Cl

(77)

AU attempts to nitrosate 77 failed.

e. AUcaline decomposition of methyl n-hutyl-N-chlorocarhamate (78) in the presence of cyclohexene.

Compound 78 i/as needed to see if a nitrene intermediate vould he formed on treatment with base. Cyclohexene \ras used as a trapping agent for the possible nitrene intermediate.

Preparation of 78 - A measured amount of chlorine was evaporated into a mixture of methyl n-butylcarbamate and water held at 15°. The lower yellow layer i/as separated and the aqueous layer was extracted with ether. The combined organic phase i/as dried over anhydrous potassium 70

carbonate. After the removal of the solvent the residue vas distilled to give 78^ of 78.

0 CI2 II CH3CH2CH2CH2 - N - C - OCIÎ3 CH3CH2CH2CH2 - N *- C - OCH3 I H2O I H C l (78)

Decomposition of 78 - A solution of 78 and cyclohexene in benzene vas treated under nitrogen vith sodium methoxide in portions. The mix­ ture vas filtered and the filtrate vas distilled to yield 50^ of methyl n-butylcarbamate. An aziridine type product vas not detected.

f. Alkaline decomposition of methyl n-butyl-N-chlorocarbamate (78).

Sodium methoxide vas added to a solution of N-chlorocarbamate in anhydrous ether. After the exothermic reaction cooled doim to room temperature, the solid vas filtered. D istillation of the filtrate gave

51.5^ methyl n-butylcarbamate. The distillate collected in the dry ice trap shotted tvo products by vpc analysis; 15^ of dimethylcarbamate and

of n-butyl cyanide.

0 0

CH3C3I2CH2CH2 -N-C - OCH3 ■ — - > CH3CH2CÏÏ2CHa -N-C - OCII3

01 01

( 78 ) + OH3OH2CH2Os N

0 II + OH3O - 0 - OOH3 71

The above reaction was repeated several times under slightly dif­ ferent reaction conditions. In each run the yield of methyl n-hutyl- carhamate was always between $0-60^.

Further investigation of this reaction should he directed towards the decomposition of compounds like methyl 4-chloropheny1-N-chlorocar- hamate whose structure is such that its decomposition cannot possibly lead to a cyanide.

Conclusions

The alkaline decomposition of 5-methyl-5-t-butyl-N-nitroso-2-oxa- zolidone (5) in methanol gave methyl trans-2, 5-trimethyl-l-buten^rl ether (36) and methyl cis-2,3;3-trimethyl-1-butenyl ether (37) in 82^ overall yield. The ratio of ^ to ,^ was (97:3)« This stereoselecti­ vity can be explained by the reaction of either an unsaturated carbene or a vinyl cation with methanol from the less hindered side of either intermediate.

Decomposition of 3 in phenol-glyme afforded 52.7^ of anisole and

43.7% of 2-methoxyethyl trans-2,3,3~trimethyl- 1-buteny 1 ether (^ ) as the major products and none of the corresponding cis-isomer. A vinyl cation intermediate seems required to explain this result. 1 5 The formation in high yields of vinyl iodides and vinyl ethers from the decomposition of 5,3-disubstituted-N-nitroso-2-oxazolidones can be explained by either a vinyl cation or an unsaturated carbene in­ termediate. However, when the 4-position of the 3,3-disubstituted-N- nitroso-2-oxazolidone is substituted with a methyl group as in the pre- 72 sent work, the yields of similar products decreased significantly. For example, decomposition of N-nitroso-i^-, 5,5-trimethyl-2-oxazolidone (48) in 2-methoxyethanol saturated with sodium iodide afforded 8.2^ of di­ methyl-2-hut anone (^ ), 7.1% of 2-methoxyethyl ^-methyl-2-hut eny 1 ether

(^ ), 22.4% of 2-methoxyethyl ^-methyl-1-huten-3-yl carbonate (^ ), and none of the expected 2-iodo-3-methyl-2-hutene (^ ). When ^ was decom­ posed in 2-methoxyethanol, only 9.8% of the vi.nyl ether ^ and 19.8% of the carbonate ^ were obtained. Since a vinyl carbene cannot be formed from the vinyl ether ^ produced must have arisen from a vinyl cation. Judging from the low yields of products isolated a trimethyl vinyl cation is much less favored than the corresponding dimethyl vinyl cation in the reactions in question.

^fhen W was decomposed in phenol-glyme, there were isolated 2.6% of the vinyl ether 5-9% of anisole and 10.6% of phenyl ^-methyl-2- butenyl ether (^ ). Though the yields of the products resulted from the cleavage of glyme were loir, these products indicate the intermediacy of a vinyl cation.

Decomposition of 1-(N-nitrosoacetylaminomethyl)cyclohexanol (6l) in diethyl ketone produced 22% of cyclohexylidenemethyl ^-pentenyl ether.

Decomposition of 6l in diisopropyl ketone gave 4.4% of cyclohexylidene­ methyl 2,4-dimethyl-^-pentenyl ether. Deconposition of ^ in cyclohexa- none gave 32% of cyclohexylidenemethyl 1-cyclohexenyl ether. Thus, in the presence of enolizable ketones decomposition of 6l generated divinyl ethers. The formation of divinyl ethers can be explained by the inter­ mediacy of either an un saturated carbene or a vinyl cation. 73

Decomposition of ^ in 2,2-dimethylpropanal yielded 4.5% of cyclo­

hexylidenemethyl t-hutyl ketone (69). Deconposition of 6l in isohuty-

raldehyde gave cyclohexylidenemethyl isopropyl ketone in 35-7% yield.

The formation of these cy, p-unsaturated ketones can he best explained hy

direct insertion of the unsaturated carhene 66^ into the aldehydic hydro­

gen-carh on hond of the aldehydes. Althougli isohutyraldehyde is enoliza-

hle, a conjugated ketone vas obtained as the product in preference to

the divinyl ether.

Treatment of 6l m th base in sodium azide and a phase transfer

agent gave az idomethyle ne cy clohexane in 56% yield. The azido function

of this vinyl azide is at the terminal carbon of the double bond. Most 34-37 of the knovm general methods of preparing vinyl azides give only

those vith the azido function at the more substituted carbon of the

double bond. The present route provides a general route to terminal

vinyl azides.

Decomposition of 6l in potassium thiocyanate yielded 39% of cyclo­ hexylidenemethyl thiocyanate. Thus, a nev synthetic route to substituted

vinyl thiocyanates has been developed.

Decomposition of 6l in triethyl phosphite gave 44.2% of cyclohexyli­

denemethyl diethyl phosphonate (70 ). This provides a nev method for the preparation of substituted vinyl phosphorates. EXPEEIMENTAL

Generalizations

1. All melting and boiling points are uncorrected. Melting points were taken with a Thomas-Hoover capillary melting point apparatus. The ther­ mometers for boiling point determination were not standardized.

2. Microanalyses were performed by the M-H-W Laboratories, Garden City,

Michigan, and Chemalytics, Tempe, Arizona.

3. Infrared absorption spectra were recorded on a Perkin-Elmer Infrared

Spectrophotometer.

4. Nuclear magnetic resonance spectra were recorded on A-60 and A-6OA nmr spectrophotometers, Varian Associates, Palo Alto, California.

5. Vapor phase chromatographic analyses were recorded on a Varian Aero­ graph, Model 1200, flame ionization gas chromatograph, and a Varian

Aerograph, Model A-90P-5 gas chromatogra%jh. A Varian Aerograph Autoprep,

Model A-700, was used for preparative vapor phase chromatography. Column

A represents 10’ x ^ / q" column of 1.0% Carbovrax 20M on Chromos orb W,

Column B represents 5’ x column of 10/S SE30 on Chromos orb W.

All vpc yields were based on the nuiriber of mole of the nitroso compounds used before decomposition.

6. U ltraviolet spectra were recorded on a Perkin-Elmer Model 202 UV spectrophotometer. 74 75 7. Mass spectra were recorded on an AEI Model MS-9 instrument by Mr.

Richard Weisenberger.

8. The phrase ‘forked up as usual" means that the reaction mixture was diluted with ice water and the products extracted into ether. The ethereal extracts were washed with a saturated salt solution^ dried by filtratio n through a cone of anhydrous magnesium sulfate or by the addi­ tion of anhydrous magnesium sulfate followed by filtratio n through a pad of Celite. The solvents were removed by distillation or on a rotary evaporator.

9. Unless othervrise specified, the nitrogen evolution usually finished as soon as all of the base had been added.

7 Alkaline Decompositions of 5-Methy 1-9-1-butyl-U -nitroso-2-oxazolidone (jj) a. Decomposition ifith sodium methoxide in methanol

A slurry of 5-59 g (O.0$ m) of N-nitrosooxazolidone $ in $0 ml of absolute methanol (freshly distilled over magnesium) was treated dropwise at 4° during 0,5 hr. with a solution of l . j 8 g (O.O55 m) of sodium methoxide in 10 ml of absolute methanol. After the theoretical amount of nitrogen had been evolved the mixture was worked up as usual. The residue was distilled to give 3.15 g (82^) of colorless materials at 63-65°/50 mm, which by vpc (column A, 40°, helium flm r 100 cc/m in ) c o n s is te d o f 97/5 of methyl trans-2,3,3~trimethyl-1-butenyl ether (^ ) and yfo of methyl cis-

2,3,3-trimethyl-1-butenyl ether (37). 76

Methyl trans-2,3-trim ethyl-1-hutenyl ether ( ^ ) : ir (neat), bands at 5.95 H (C=C), 8.90 p, (C=C-0CH3); nmr (CCI4), T 6 .9 8 ( s , 9, t-B u ), T

8.45 (d, J = 1 Hz, 3, CHs), T 6.49 (s, 3, -OCH3), T4.27 (m, J = 1 Hz, 1,

=CH); mass spectrum, mol. vt. 128, exact mass measurement: 128.1202

(calcd value = 128.1201).

Anal. Calcd for CgHieO: C, 74.9; H, 12.6.

Pound: C, 7 4 .9 ; H, 1 2 .6 .

For further characterization, a 2,4-dinitrophenylhydrazone, mp 125-

126°, vas prepared; mass spectrum, mol. -vrt. 294.

Methyl cis-2,5,5-trimethyl-1-butenyl ether (^ ) showed nmr (CCI4),

T 8.89 (s, 9, t-Bu), T 8.52 (d, J = 1.5 Hz, 3. CHs), T 6.54 (s, 3; -OCH3),

T 4 .4 2 (m, J = 1 .5 Hz, 1, =CH). b. Decomposition vith sodium phenoxide in phenol-Rl;

To a stirred solution of 5*1 g (0.044 m) of sodium phenoxide and

33.6 g (0.4 m) of phenol in 20 g of glyme vas added dropvise at room temperature during 5 min a solution of 7.45 g (0.04 m) of 5-methyl-5-t- butyl-N-nitroso-2-oxazolidone (5) in I6 g of glyme. The evolution of nitrogen vas very slov. The theoretical amount vas obtained only after

18 hr. After the usual vork-up vhich included four vashes vith lO'^ KOH, distillation gave three fractions. Preparative vpc (column A, helium flov 150 cc/min) gave pure materials from each of the fractions described b e lo v .

Fraction 1 (78-103°): column temp. 50°, 1.4 min, 0.297 g (7.7%) of 2,2-dimethyl-3-pentyne (43). c=c

3.0 4.0 5.0 6.0 7.0 8.0 9.0

Figure 1 - Kinr spectrum, 60 MHz, of ^ in CCI4

- 4 78

Fraction 2 (48-108°/20 nun): column temp. ]10°, A, 5*5 min, 2.28 g

(52.7'^) of anisole; B, 4.7 min, 5*15 g (45.7^) of 2-methoxyethyl trans-

2,3^3-trlm ethyl-l-hutenyl ether (4l).

Fraction 3 (96°/0.4 mm): column temp. 150°, A, 7 min, 0,179 g (2.2^) of phenyl 2,3 ^ 3-tr Imethyl-1-hut eny 1 ether (^ ); B, 10 min, 0.921 g (ll.3%) of 2-phenoxymethyl 3^3-âlmethyl-l-hutene (45).

In addition to the ahove fractions, 0.3 g (4.8%) of the 5-methyl-5- t-hutyl-2-oxazolidone vas recovered from the residue hy recrystalllzatlon from henzene-Skellysolve B.

2,2-Dlmethyl-3“pentyne (^ ) : same vpc retention time and nmr as authentic sample, nmr (glyme), T 8 .8 5 ( s , 9, t-B u ), T 8.32 (s, 3; =C=CH3),

T 6.71 (s, CH3O-), T 6.55 ( s , CH3OCTI2CH2OCH3).

2-Methoxyethyl trans-2,3,3-trlmethyl-l-hutenyl ether (4l): Ir (neat), hands at 6.00 p. (C-C), 8.58 p,, 8.92 p,; nmr (CCI4), T 8.97 (s, 9, t-Bu),

T 8.45 (d, J = 1.5 Hz, 3, CH3C=), t 6.67 (s, 3, -OCH3), T 6.10-6.63 (tvo groups of hroad peaks, -OCH2CH2-OCH3), T 4 .1 3 (m, 1, =CH); mass spectrum , mol. vt. 172.

Anal. Calcd for C10H20O2: C, 69.8; H, 11.6.

Found: C, 7 0 .1 ; H, 1 1 .8 .

Phenyl-2,3^3-trlm ethyl-l-hutenyl ether (h2): Ir (neat), hands at

6.05 p, (C=C), 6.30 p, (aromatic C=C), 8.15 p,, 9.20 p,, 13-35 pL, 14.58 p.; nmr (CCI4), T 8.82 (s, 9, t-Bu), t 8.26 (d, J = I.5 Hz, 3, CH3C=), T 3.69

(m, 1, =CH), t 2.50-3.20 (m, 5; aromatic); mass spectrum, mol. -vrt. I90.

2-Phenoxyraethyl 3;3-dimethyl-1-hutene (45): Ir (neat), 6.10 p, (C=C),

6.25 p, (aromatic C=C), 8.12 p,, 13-35 pi; 14.58 p; nmr (CCI4), T 8.86 (s, 9, 79 t- B u ) , T 5 .5 1 (m, J = 1 Hz, 2, -CHâ-OPh), T k.96 (m, J = 1 Hz, 1, =CH),

T 4 .8 7 (m, J = 1 .5 Hz, 1, =CH), t 2.65-3.35 (m, 5, aromatic); mass spec­ trum, mol. vt. 190.

Anal. Calcd for Ci s Hiq O: C, 8 2 .1 ; H, 9-5-

Found; C, 8 2 .1 ; H, 9.6.

Preparation of H-Hitroso-4,5,3-trimethyl-2-oxazolidone (48).

Ethyl 2,3-dimethyl-3-hydroxybutanoate (49). - - 5 6 A mixture of 13O g (2.0 m) of activated zinc and 300 ml of benzene

( 56) L. F . F ie s e r and W. S. Johnson, J . Amer. Chem. S o c ., 62, 576 (1940).

vas brought to reflux. After 50 ml of benzene had been distilled, a solution of 105 g (1.8 m) of acetone in 25O ml of ether vas added. To the refluxed vell-stirred mixture vas added dropvise 3^2 g (2.0 m) of ethyl Q^bromopropionate during 3 hr. After one additional hour of re­ flux the mixture \ib.s cooled to room temperature, and then hydrolyzed in

1.5 of 10^ hydrochloric acid. The mixture \ras vorked up as usual and the residue vas distilled to give 2l4 g (74^) of kO, bp 77-78° (lO mm); ir (neat), bands at 2.8 p (-0H), 5.80 p, 5.85 p (C=0).

Anal. Calcd for CgHieOs: C, 6O.O; H, 10.0.

Found: C, 59.9; H, 10.1.

2,3-Dimethyl-3-hydroxybutanoic Acid Hydrazide (50).

To 194 g (1.21 m) of the hydroxy ester h9 cooled in an ice bath vas added 57.5 g (I.8 m) of anhydrous hydrazine. The mixture solidified at CM- 1500 1000 9004000 3000 2 0 0 0 1500 1000 9004000 890 700 100 I"""'"' 0.0

2 0 - =10

WAVELENGTH (MICRONS)

Figure 2 - Infrared spectrum of CHa^ /CHa C. / H CHa ^ C — C / O-CSs^ 0^ CHa CHg CHa

A J W y _v ,A_

3.0 4.0 5.0 6.0 7.0 8.0 9.0 lO.Of

Figure 3 - Kmr spectrum, 60 MHz, of ^ in CCI4

CO H CM- 4 0 0 0 3 0 0 0 2000 1500 1000 900 800 700 lOO-r-^— i— 0.0

8 0

-,2c d 60- CO o -.3 2

Ph 2 0 - =10

WAVELENGTH (MICRONS)

F ig u re k - Infrared spectrum of ^ 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0

Figure 5 - Nmr spectrum, 60 MHz, of in CCl^ 84 room tenç)erature after 24 hr and the excess hydrazine was removed in a vacuum desiccator over concentrated sulfuric acid. Recrystallization from 95^ ethanol-chloroform afforded 112 g (63^) of ^ as a white cry­ stalline solid; rap 124-125°.

A n al. C alcd f o r CGHi^NgOg: C, 4 9 .3 ; H, 9.6.

Found: C, 4 9 .5 ; H; 9.6.

4; 5) 5-Trimethyl-2-oxazolidone ( ^ ) .

A solution of 4 l.4 g (0.6 m) of sodium nitrite in 120 ml of water was added dropmse at 5° during 3 hr to a stirred solution of 73.1 g (0.5 m) of the hydrazine ^ in 25O ml of 2N hydrochloric acid. The mixture was extracted with henzene-chloroform (3:l). The extract (kept cold at .57 all times; was washed with a saturated sodium chloride solution and then

(57) The extract decomposed very readily at room temperature.

added into 100 ml of refluxing benzene during 2 hr. After the removal of the solvents on a rotary evaporator the residue was distilled at 105°/0.15 mm. Recrystallization from benzene-Skellysolve B afforded 54 g (83%) of oxaz olidone rap 61.O-61.5°; ir (KBr), 3*05 M- (-RH), 5.77 M- (C=0); nmr

(C D C I3); T 8.80 (a, J = 7 HZ; 3, -CHCH3); T 8.64 (s, 3, -C H 3); t 8 .5 2

( b , 3; -C H 3 ), T 6.30 (q , J = 7 Hz, 1, ΠC H 3), T 3 .5 2 (m, 1, M l).

A n al. C alcd f o r CoHiiMOg: C, 55-8; H, 8 . 5.

Found: C, 56.0 ; H, 8 . 7 . 85 N-Nitroso-4,5, 5"trim ethyl-2-oxazolidone ( ^ ) .

To a stirred solution of k2 g (O.525 m) of oxazolidone _51 in I50 ml

of 6U hydrochloric acid was added drqptrise at 5° a solution of 26.8 g

(0.390 m) of sodium nitrite in 100 ml of water. The yellow precipitate

was collected; washed thoroughly with cold yratev, and then dried vacuo

over phosphorous pentoxide. Recrystallization from ether-pentane afforded

4%.7 g (93^) of yellcrtr N-nitroso-4,5; 5-trim ethyl-2-oxazolidone (W ); mp

86-89°; ir (KBr); 5.57 p (c=0).

Alkaline Decompositions of N-Nitroso-4;5;5-trimethyl-2-oxazolidone (48).

a. in 2-methoxyethanol containing sodium iodide.

A 20% solution of sodium 2-methoxyethanolate in 2-methoxyethanol

(20 g) was added dropvrise during 10 min to a w ell-stirred solution of 2.37

g (0.015 m) of nitrosooxazolidone ^ in 50 nil of 2-methoxyethanol satura­

ted with sodium iodide (18 g/50 ml). The theoretical amount of nitrogen

was evolved in 10 min. The temperature tos maintained helovr 30° hy cool­

ing with an ice-irater hath. The mixture was worked up as usual. Two

fractions were collected hy distillation. Pure samples were obtained hy

preparative vpc (column A).

Fraction 1 (35-70°/35 mm): column temp. 100°; helium flow 100 cc/

min; < 1 min; 0.091 g (8.2%) of 3-methyl-2-hutanone (52).

Fraction 2 (85-122°/35 mm): column temp. 132°; helium floiv 100 cc/

min; A, 1 min; O.153 g (7.1%) of 2-methoxyethyl 3-methyl-2-huteiiyl ether

(55); B; 3.5 min; O.63I g (22.4%) of 2-methoxyethyl 3-methyl-l-huten-3- yl carbonate (54). 86

5-Methyl-2-butanone (^ ) vas identified hy comparison with the in­

frared spectrum and .the 2,4-dinitrophenylhydrazine derivative of the

authentic sample.

2-Methoxyethyl 3-methyl-2-hut eny 1 ether (_^) : ir ( neat ), 5*93 M-

(C=C); 8.52 M- (C=C-0-), 8.85 (J,; nmr (CCI4 ) T 8.45 (hroad singlet, 6,

(CH3)2C=), t 8.26 (hroad singlet, 5, =((^3)0-0), T 6.69 (s, 5, -OCH3),

T 6.5O-6.57 (complex m ultiplet, 4, -OCEgCHg-OCH3); mass spectrum, mol.

wt. l44, exact mass measurement 144.1152 (calcd. l44.II50).

For further characterization, a 2,4-dinitrophenylhydrazone, nç) 1 1 9 -

120°, was prepared: mass spectrum (mol. -vrt. 294) identical to that pre­

pared from 5-methyl-2-hutanone.

2-Methoxyethyl 5-methyl-l-huten-5-yl carbonate ( ^ ) : ir (neat),

5.75 M- (C=0), 6.10 p (C=C, weak hand), 7.90 p, 8.80 \x; nmr (CCI4), T 8.48

(s, 6, (CH3)2C), t 6.68 (s, 5, -OCH3), T 5.74-6.60 (complex m ultiplet,

4 , -OCH2 CH2 OCH3 ) , T 5 . 6 5 - 9 .10 (m ultiple peaks, -CH-CH 2 ); mass spectrum,

mol. w t. 188.

A n a l. C alcd f o r C 9 H1 6 O4 : C, 57.4; E, 8 . 6 .

Found: C, 57.4; H, 8.6. h. with sodium phenoxide in phenol-glyme.

To a s t i r r e d s o lu tio n o f 5»57 g (0.048 m) of sodium phenoxide and

55.6 g (0.4 m) of phenol in 16 g of glyme -vra.s added dropwise a solution

of 6.55 g (0.04 m) of nitrosooxazolidone 48 in 20 g of glyme. The theore­

tical amount of nitrogen was obtained in 2 hr. The temperature was main­

tained helovr 50°. After the usual vrorkup (2 vrashes vrith 3^% sodium

hydroxide) distillation at 70-117°/55 mm afforded 2.6l g of colorless CM- 4000 3000 2000 15001000 900 8Ç0 700 100 0.0

80-

60-

C=C 20 - -.7 =10

WAVELENGTH (MICRONS)

Figure 6 - Infrared spectrum of 53 CM- 7 004000 3000 2000 1500 1000 900 800 7004000 100 I...... 0.0

80-

-,2 cd

k4z -,5rn 0 - C - Ü -.6 20 - =10

WAVELENGTH (MICRONS)

Figure 7 - Infrared spectrum of ^

00 CO CH2 O - C - 0 CHs CH2

CH.

3.0 4.0 5.0 6.0 7.0 8.0 9.0

Figure 8 - Kmr.spectrum, 60 MHz, of 5^- in CCl^ 90 products which hy vpc (lO' x column of 3% Carbowax on Chromosorb \1, l40°) helium flow 100 cc/min) showed many components but only three were identified: k, 1.2 min, 0.15 g (2.6'^S), 2-methoxyethyl 5-methyl-2-butenyl e th e r ( ^ ) ; B, 1.5 min^ 0.168 g (3*9^) anisole; C, 1.7 min, 0.687 g

(l0.6%) phenyl 5-™ethyl-2-butenyl ether (6o).

Phenyl 3“inethyl-2-butenyl ether (6o): ir (neat), 5-92 p, (C=C), 6.25 p, (aromatic C=C), 8.20 p,, 8.69 p., 13-25 p., l4.48 p,; nmr (CCI4 ) , T 8.4 2

(s, 5, trans CHs-C^C-OPh), T 8.28 (broad singlet, 6, cis CH3-C=C-0Ph and

=C(CM3)0Ph), T 2.68-3.40 (m, 5, aromatic); mass spectrum, exact mass measurement m/e l62.1046 (calcd. m/e l62.1045).

Anal. Calcd for C11H14O: C, 8l.4; H, 8.7.

Found: C, 8 1 .2 ; H, 8 . 9 . c. with 2-metho%yethoxide.

A 20^ solution of sodium 2-methoxyethoxide (O.O36 m) in 2-methoxy- ethanol was added dropwise to a solution of 4.73 g (0.03 m) of nitroso- oxazolidone ^ in 45 ml of 2-methoxyethanol. After the theoretical amount of nitrogen was collected (in 0,5 hr) the mixture was worked up as usual.

D istillation at 31-120° (lO mm) yielded 2.46 g of products which by ypc

(column A, l40°, helium flow 100 cc/min) showed many components besides the solvent peak, but only two were isolated and identified: A, 3 min,

0 .4 l6 g {9.6%) of 2-methoxyethyl 3-methyl-2-butenyl ether (^ ) and B,

4 min, 1.12 g (19.8%) of 2-methoxyethyl 3“inethyl-l-buten-3-yl carbonate

(5 4 ). CM- 4000 3000 2000 1500 1000 900 800 700 100 — 0.0

80-1

-.200 60 - CO o -.3 3

CH; OPh 20 - C = C =10

WAVELENGTH (MICRONS)

Figure 9 - Infrared spectrum of 60

VO H 92

Alkaline Decomposition of 1-(N-Nitrosoacetylaminomethyl)cyclohexanol 23 (61) in the Presence of Ketones.

Decomposition in diethyl ketone.

To a stirred solution of 4.9 g (0.02^5 m) of nitrosoamide 6l in 25 24 ml of pentane containing 0.6 g of Aliquat 336 and 21 ml of diethyl ketone vas added dropvise at -10° during 10 min a ^0% solution of sodium hydroxide in irater. After the nitrogen evolution had stopped ($0^ of the theoretical amount), the mixture \ms poured into 100 ml of a saturated

sodium chloride solution and vorked up as usual. D istillation at 40-8?°/

0.05 mm furnished l.T g of colorless products which by vpc (column B, helium flow 75 cc/min) shovred five components: A, 1.5 min, O.13 g (5.4%) oyclohexanone; B, 2 min, O.I5 g (5.4^) cyclohexanecarboxaldehyde; C, 2.5 min, 0.16 g (5.6^) cycloheptanone; D, 6 min, O.38 g (lO^) acetoxymethyl- 58 enecyclohexane (§2) ; E, 11 min, O.99 g (22^) cyclohexylidenemethyl 3-

(58) Mousseron, Jacquier, W internitz, Comp. Rend., 224, I23O (1947).

pentenyl ether (79). Pure materials were obtained by preparative vpc on the above column.

Oyclohexanone, cyclohexane carb oxaldehyde, and cycloheptanone were identified by comparison of ir and vpc retention time with the authentic sam p les.

Acetoxymethylenecyclohexane (62): ir (neat), bands at 5-70 p (C=0),

5 .9 0 [I (C=C); nmr (CCI4 ) , t 8.4 0 ( s , 3, CÎI3), t 7 .9 3 ( s , 6, -CH g-), t

3 .1 3 ( s , 1, =CH). 93

Anal. Calcd for C9H14O2: C, 7 0 .1 ; H, 9 .2 .

Found: C; 7 0 .0 ; H, 9.h.

A 2,4-dinitrophen;Alhydrazone, mp l66-l67°; vas prepared -tdiich shov;ed identical mass spectrum to that prepared from eyelohexanecarb oxaldehyde

(m /e 292).

Cyclohexylidenemethyl 3-pentenyl ether (72): vapor phase chromato­ graphic analysis in a different column (iC x ^/b" 5^ SE $0 on ®°/ao

Chromosorh ¥, 138°, F and M Model 609 Flame Ionization Gas Chromatograph) showed two components with very close retention time in the ratio of 53: hj, possibly a mixture of cis and trans isomers. Infrared spectrum

(neat), 5.95 p (C=C), 8.40 p (C-O-C); nmr (CCI4), T 8.97, t 8.92 (2 trip ­ l e t s , J = 7 Hz, 3; CÏÏ2CH3), T 8.42 (m, 9, -CH2- and CHgC^C), T 7 .9 0 (m,

6, CH2C=), t 5.50, T 5.35 (2 quartets, J = 7 Hz, 1, CHgCH-), T 4 . l4 (m,

1, =CH); mass spectrum, mol. wt. I80, exact mass measurement I8O.I515

(calcd. 180.1514).

For further characterization, a drop of 1^ hydrochloric acid \ra.s added to the divinyl ethers and the resultant mixture was subjected to vpc analysis. The retention time of the major peaks and the nmr spectrum of the mixture indicated a mixture of cyclohexanecarboxaldehyde and diethyl ketone. Mass spectrum of the 2,4-dinitrophenyIhydrazine deriva­ tives showed peaks at m/e 266 and m/e 292, corresponding to those derived from diethyl ketone and cyclohexanecarboxaldehyde.

Decomposition in diisopropyl ketone.

To a stirred solution of 2.5 S (0.0125 m) of nitrosoamide 6_1 and l4 .3 g (0.125 m) of diisopropyl ketone in 20 ml of pentane containing 0.5 g of 9h

Aliquat ^$6 was added dropwise during O.5 hr a 3^% solution of sodium hydroxide in "v/ater. The temperature "vras maintained helovr 10°. After the theoretical amount of nitrogen had "been evolved (in 0.5 hr) the mixture was poured into 5O ml of a saturated sodium chloride solution and worked up as usual. The residue was distilled at 29-125°/0.01 mm to afford

1 g of colorless liquid which hy vpc (column B; 165°, helium flcrtr 75 cc/ min) shcn-red several components, hut only two were isolated: A, 2 .5 min,

0.30 g (15.5^) acetoxymethylenecyclohexane (§2); B, 8 m in, 0 .1 2 g {h.h%) cyclohexylidenemethyl 2,4-dimethyl-3-pentenyl ether (80).

The divinyl ether % has ir (neat), hands at 6.00 p, (C=C), 8.^5 P;

8.70 p, 8.95 nmr (CCI4), t 9.00 (d, J = 7 Hz, 6, -011(0^3)2), t 8.58

(m, 12, -CH2 - and =C(CH3 )g ) , T 8 .0 2 (m, 2, t r a n s -CH2-C=C-0- ) , T 7 .7 8

(m, 2, cis -CH2-C=C-0-), t 7.18 (m, 1, -Cg(023)2), T 4.34 (m, 1, =CH), mol. wb. 208 (mass spectrum).

Anal. Calcd for C14H24O: C, 80.7; H, 11.6.

Found: 0, 80.4; H, 11.6.

Decomposition in oyclohexanone.

A 50^ solution of sodium hydroxide in tra.ter was added dropwise at

3° in 25 min to a w ell-stirred solution of 5.O g (0.025 m) of nitroso­ amide 61 and 19.6 g (0.2 m) of oyclohexanone in 30 ml of pentane contain­ ing 1 g of Aliquat 338. The temperature was maintained helovr 10°. After the evolution of the nitrogen gas (95^ of the theoretical amount) the mixture was poured into 100 ml of saturated sodium chloride solution and worked up as usual. D istillation at 60-94°/0.05 mm afforded 2.1 g of CM- 4000 3000 2000 15001000 900 800 700 100 0.0

8 0 -

-,2 cd CO o -.32

20 - o<: =1.0

I 1 I I I ' 8 9 10 WAVELENGTH (MICRONS)

Figure 10 - Infrared spectrum of ^

VO VJl 96

colorless products. Vapor phase chromatograph (column B, 158°^ helium

flow 120 cc/min) shovred two main components: A, 1.7 min, O.I9 g {5%)

acetoxymethylenecyclohexane (62)} B, 7 m in, 1 .6 g i'^2.%) cyclohexylidene­ methyl 1- cyclohexenyl ether (^ ). Pure materials were obtained by pre­ parative vpc on the above column.

The infrared spectrum of cyclohexylidenemethyl cyclohexenyl ether

shovred bands at 6.00 p (C=C) and 8.5O p,; nmr (CCI4 ), T 8 .4 4 (m, 10, -C H g-),

T 7.92 (m, 8, CÏÏ2C=), T 5 .2 8 (m, 1, = 0 5 -0 ), T 4.10 (m, 1, =0H-0); mass spectrum, exact mass measurement 192.1^14 (calcd. value: I92.I516).

Anal. Oalcd for O13H20O: 0, 81.5; H, 10.5.

Found: 0, 81.5; H, 10.5.

Allcaline Decomposition of 1-(5-Nitrosoacetylaminomethyl)cyclohexanol

(61) in the Presence of Aldehydes.

Decomposition in 2,2-dimethylpropanal.

A 50^ solution of sodium hydroxide in water was added dropwise at

-15° during 0.5 hr to a w ell-stirred solution of 2.5 6 (0.0125 m) of nitrosoamide 6l and 4.4 g (O.O5I m) of 2,2-dimethylpropanal in I5 ml of pentane containing O.75 g of Aliquat 536. The theoretical amount of nitrogen was evolved. The temperature was maintained belo^f -5°. The mix­ ture was then poured into 75 ml of a saturated sodium chloride solution and worked up as usual. D istillation at 57-100°/0.04 mm afforded O.7 g of colorless products "vrtiich by vpc (column B, 155°; helium flow I50 cc/ min) shovred several components, but only two were isolated and charac­ terized: A, 0.5 min, O.585 g (27.5^) cyclohexanecarboxaldehyde; B, 4 min. CM- 2000 1500 1000 900 800 700 100 0.0

80 -

20 - =10

WAVELENGTH (MICRONS)

Figure 11 - Infrared spectrum of 8l

\o 3.0 4.0 5.0 6.0 7.0 8.0 9.0 IC.Ot

Figure 12 - Itor spectrum, 60 MHz, of 8l in CCI4

VO CO 99

0.1 g (4.5^) cyclohexylidenemethyl t-hutyl ketone (TO).

The infrared spectrum of the conjugated ketone 70 shovred hands at

5.87 d, 5.98 [i, and 6.20 p, (C=C); nmr (CCI4 ) , T 8 .8 7 (s , 9 , t- B u ) , T

8 .3 6 (m, 6 , -C H g-), T 7 .8 0 (m, 2 , CHaC^), t 7 .2 5 (m, 2 , CH2C=), t 3 .7 9

(m, 1; =CH); mass spectrum, mol. vt. I80, exact mass measurement, I8O.I517

(calcd. value: 18O.I519); UV (ahs. EtOH), 24l mp, (e 12,700).

Anal. Calcd for C12H20O: C, 79-94; H, 11.17.

Found: C, 8 0 .2 5 ; H, 1 1 . 0 9 .

For further characterization, a 2,4-dinitrophenylhydrazone, mp 125-5“

127.0°, was prepared: mass spectrum, mol. -vrb. 36O.

Decomposition in isohutyraldehyde.

To a stirred solution of 2.5 g (0.0125 of nitrosoamide 6 l and 9 g

(0.125 m) of isohutyraldehyde in I5 ml of pentane containing 1 g of Ali­ quat 356 was added dropwise at -10° a ^0% solution of sodium hydroxide in water. The theoretical amount of nitrogen was collected in I5 min.

The mixture \ra.s then poured into 75 nil of a saturated sodium chlorid e solution and worked up as usual. D istillation at 60-137°/0.2 mm yielded

2.18 g of colorless product. From the preparative vpc (column B, 125°; helium flow 120 cc/min, retention time 5-5 min) there 'vras isolated 0.74 g (35.7^) of cyclohexylidenemethyl isopropyl ketone (02), ir (neat),

5.94 (C=C), 6.15 p, (C = 0), and 6.90 p (doublet (CH3 ) 2 CH -); nmr (CCI4 ),

T 8 .9 7 (d , J = 7 Hz, 6 , - 011( 013)2 ), T 8 .3 8 (m, 6 , -CH2 - ) , x 7 .8 4 (m, 2,

CH2C=), t 7 .3 6 (m, J = 7 Hz, 1, -CH(013)2), x 7.26 (m, 2, CH2C=), x 4.10

(m, 1, =01); UV (ahs. Et OH), 24l mp ( e 11,200); mass spectrum, m/e at

166, 123, 9 5 . 100

Anal. Calcd for CnHiaO: C. 79.5; H, 10.9.

Found: C, 7 9 -2 ; H, 1 1 .1 .

For further characterization a 2;4-dinitropheny1 hydrazone, up

127.9-128.0°; mass spectrum, mol. \rt. $46, vas prepared.

Preparation of Cyclohexylidenemethyl t-Butyl Ketone (69). — Triethyl phosphonoacetate.

To 70 g (0.42 m) of triethyl phosphite vas added drop vise 70 g (0.42 m) of ethyl hromoacetate in 1. 5 hr. The mixture vas heated to 90° and ethyl bromide vas distilled. The mixture vas then heated at 165-170° for 9 hr. The residue vas distilled to give 69 g (73^) of triethyl phos- 52 phonoacetate, bp l64°/25 mm (reported bp IO9-IO9.5°/0.80 mm), ir (neat),

5.78 p (C=0), 9.80 p, (P-O-C); nmr (CCI4), T 8.71 (t, J = 7 Hz, 3,

-COOCH2CH3 ), T 8.66 (t, J = 7 Hz, 6, (CH3CH20)2P(0)-), T 7.15 (a, J = 22

Hz, 2, -P(o)CH2C(o)-), t 5.89 (m, J = 7 Hz, 6 , -CH2CH3).

S3 Ethyl Cyclohexylideneacetate.

A 2.9 g (0.07 m) sample of a suspension of 58.2^ sodium hydride in mineral oil \ tsls vashed repeatedly vith hexane and the remaining sodium hydride vas suspended in 25 ml of benzene vhich had been dried by f il­ tering through sodium hydride. To this suspension \ras added dropvise during 0.5 hr 17.9 g (O.O8 m) of triethyl phosphonoacetate under a nitrogen atmosphere. The mixture became milky then changed to a clear light yellovr solution. The resulting solution vas stirred for 0. 5 hr and then 6.85 g (O.O7 m) of oyclohexanone vas added dropvise in I 5 min.

The temperature vas maintained at 30-55° 'vrlth an ice-vat er bath. A gel- CM- 4000 3000 2000 1500 990 800lopo 700 too I...... 0.0

-,2c d CO O - 3 3

20 - -.7 =10

WAVELENGTH (MICRONS)

Figure IJ - Infrared spectrum of 82

; CH; CH

4.0 5.03.0 6.0 7.0 8.0 9.0

Figure - Itor spectrum, 60 MHz, of ^ in CCI4

ë ro 103 like material precipitated. The mixture vas heated at 60-65° for 15 min, cooled to room temperature and the gel-like precipitate vas separa­ ted and vashed vith three portions of 25 ml of hot benzene. The combined benzene solution vas concentrated on a rotary evaporator and the residue vas distilled to yield 7.8 g (6T^) of ethyl cyclohexylideneacetate, bp 53 U5°/l5 mm (reported bp 48-49 /0 .02 mm). The product vas of > 95^ purity by vpc analysis (column B, 135°) and had infrared absorption bands at 5'85 H (conjugated ester C=0) and 6.10 p (conjugated C=C); nmr (CGI4)

T 8.75 (t, J = 7 Hz, 3) -CH2CH3), T 8.36 (m, 6, -CH2-), t 7 .8 0 (m, 2,

-CH2 C=), T 7 .1 6 (m, 2, -CH2C=), t 5.91 (q, J = 7 Hz, 2, -C ^ - C lls ) , T 4 .4 7

(m, 1, =CH).

Cyclohexylideneacetic acid.

To a solution of 1.84 g (O.0458 m) of sodium hydroxide in 10 ml of ethanol containing a small amount of vater (enough to make the solution homogeneous) tos treated vith 7 g (0.04l6 m) of ethyl cyclohexylidene­ acetate. The mixture iras heated at 70° for 3 hr. After the mixture had been cooled to room temperature 10 ml of irater vas added. Ethanol iras removed on the rotary evaporator and the resulting solution vas acidified vith 10^ hydrochloric acid. The vhite solid vas collected and dissolved in ether. After the usual vork-up there vas obtained 5 g (86^) of lAiite 5 9 product, mp 87.0-88.5 (reported mp 89 ), ir (neat), 3-0 p (associated

(59) 0. W allach, A nn., I 5I ( 19OO). 104

oh), 6.0 (J, (conjugated 0=0) and 6.15 M- (conjugated C=C); nmr (CCIa ),

T 8.3 4 (m, 6, -CHs-), t 7 .7 3 (m, 2, -CH2-C =), t 7 .1 2 (m, 2, -CH2 -C =),

T 4.38 (m, 1, =CH), t - 2 .3 0 ( s , 1 , -COOH).

60 Cyclohexylidenemethyl t-Butyl ketone (69).

(60) Procedure follovred that from H. 0. House, W. L. Respess, and G. M. I-Thitesides, J. Org. Chem., 3128 (1966).

To a veil-stirred solution of 1.4 g (O.Ol m) of cyclohexylidene- acetic acid in 20 ml of dry ether -vra-s added under a nitrogen atmosphere vith a syringe 20 ml of 1.29 N (0.0248 m) solution of t-hutyllithium in hexane at 2° over a period of 1.5 hr. The mixture vas stirred for an additional 11 hr 'vrith the temperature maintained helovr 10°, then poured

into an ice cold ammonium chloride solution foUcnred hy ether extrac­ tion. The ethereal extract vras vorked up as usual. From the preparative vpc (column B, 132°, helium flov, I36 cc/min, retention time 2 min) there 'vra.s isolated O.85 g (47^) of cyclohexylidenemethyl t-hutyl ketone

(69) vith ir, nmr, and uv identical "vrith that obtained from the decon^)0-

sition of the nitroso amide 6l in 2,2-dim thy 1 propanal.

Decomposition of l-(H-Nitrosoacetylaminomethyl)cyclohexanol (^ ) vith

Triethylamine in the Presence of Isohutyraldehyde.

A solution of 2.5 g (0.0125 ci) of nitrosoamide 6l and 9 g (0.125 m) of isohutyraldehyde in 20 ml of pentane vas treated dropvise at 0° 'vrLth

1.68 g (0.0166 m) of triethylamine during 15 min. The mixture vas stirred 105

a t 1 0 -1 2 ° fo r 1.5 hr. After the evolution of nitrogen was coznplete the

mixture was poured into a saturated sodium chloride solution and worked

up in the usual manner. D istillation at $4-69° (O.O5 mm) yielded 0.8 g

of products which hy vpc (column B, 1$5°; helium flovr 1$6 cc/min) shcrvred

two main components: A, 2 min, 0.208 g (l5^) of acetoxymethylenecyclo­

hexane ( 62) and B; 4 min, 0.200 g (12.6^) of cyclohexylidenemethyl iso­

propyl ketone (82).

Alkaline Decompositions of l-(h-Nitrosoacetylaminomethyl)cyclohexanol

(61) in the Presence of Nucleophiles,

a. sodium aside.

To a stirred mixture of 10 g (0.154 m) of sodium aside in 25 ml of water containing 1 g (0.025 m) of sodium hydroxide and 0.5 g of Aliquat

356 was added dropirise at 3° 8. solution of 2.5 g (0.0125 m) of nitroso­

amide ^ in 20 ml of pentane. After the evolution of nitrogen (quanti­

tative in 15 min) the mixture was worked up as usual. The crude unsatura­ ted aside (2.2 g) \ras p u r i f i e d hy p a s s in g th ro u g h 30 g o f n e u tr a l Woelra

alumina oxide activity grade I with hexane. After the removal of the

solvents vacuo 0.95 g (56^) of asidomethylenecyclohexane was produced

as a yellow liquid, ir (neat), 4.75 M- (=C-N3), 6.00 p, (C=C); nmr (CCI4),

T 8 .4 8 (m, 6 , -CPI2- ) , T 7 .9 2 (m, 4, CHaC^), T 4 .l 6 (m, 1, =CH).

A n al. C alcd f o r C7H11N3: C, 6 1 .3 ; H, 8 .1 ; N, $ 0 .6 .

Found: 0, 6l.4; H, 8.2; N, 30.8.

The analytical sample was obtained hy hulh to hulh distillation at room temperature and 0.1 ram. CM-' 4 0 0 0 3 0 0 0 2000 1500 7 0 0 1001""""'I ' ' ' 0.0

80-

LJ 60-

z

20 - -.7

- 1.0

WAVELENGTH (MICRONS)

Figure 15 - Infrared spectrum of azidomethylenecyclohexane

ë o\ 5 .0 4 .0 5 .0 6.0 7 .0 8.0 9 .0 10. OT

Figure l 6 - Nmr spectrum^ 60 MHz^ of azidomethylenecyclohexane in CCI4

g 108

t. potassiiun thiocyanate.

To a stirred mixtvire of 12.1 g (0.125 ci) of potassium thiocyanate,

0 .7 5 B (0.0185 m) of sodium hydroxide, 8 g of water, and O.5 g of Ali­

quat 356 was added dropwise at 5-7° a solution of 2.5 g (0.0125 m) of

nitrosoamide ^ in 25 ml of pentane. After the quantitative amount of

nitrogen had heen collected (in 15 min), the aqueous layer was extracted

with ether and the comhined organic phase was worked up as usual. Dis­

tillatio n of the residue (2.25 g) at 68-80°/0.15 mm yielded O.78 g (h-lfj)

of colorless cyclohexylidenemethyl thiocyanate (> 95^ pure hy vpc). The

analytical sample ■vra.s obtained by preparative vpc (column A, l40°, helium

flow 100 cc/min, retention time 5 min). Infrai-ed spectrum (neat), bands 61 at 4.65 p. (=C-SCN, sharp band), 6.20 p, (C=C, weak band); nmr (CCI4),

(61) E. Lizber, C. N. R. Rao, and J. Ramachdran, Spectrochimica Acta., Vol. 13, p 296 ^ 959).

All the organic thiocyanates show a sharp strong peak due to the nit rile stretching around 4.67 p,; 2l40 cm“^ as compared to a broad and very strong band centered around 4.78 p, 2100 cm“^ for organic isothiocyanates.

T 8.39 (m, 6, -C R g-), T 7.70 (m, 4 , CIfe-C=), T 4.28 (m, 1, =Ch); mol.

wt. 153 (mass spectrum).

Anal. Calcd for CqHuNS: C, 62.7; H, 7.2; N, 9-1; S, 20.9.

Found: C, 62.6; H, 7.1; R, 9-3; S, 20.9.

c. sodium iodide.

A solution of 2.5 g (0.0125 m) of nitrosoamide in I5 ml of pentane was added dropwise during 25 min to a stirred mixture of 20 g (O.138 m) CM' 40,00 3 0 0 0 2000 1500 7 0 0 100 I'" " " " ' ' ■ ' 0.0

80- w -,2cd 60- (J) o -.32

20 - C k s-c = =10

WAVELENGTH (MICRONS)

Figure 17 - Infrared spectrum of cyclohexylidenemethyl thiocyanate

§ 4.0 6.0 7.0 8.0 9.0 10. OT

Figure l8 - I#r spectrum, 60 MHz of cyclohexylidenemethyl thiocyanate in CCI4 ë I l l of sodium iodide^ 1 g (0.025 ™) of sodium hydroxide, 0.75 g of Aliquat

356, and 10 g of -water at 3-5°. After the quantitative amount of nitro­ gen had heen evolved the mixture was worked up as usual. D istillation afforded 2.0 g (72%) of iodomethylenecyclohexane, hp 30-30.5°/0.15 mm, nmr (CCI4 ), t 8 .4 6 (m, 6 , -CHg-), t 7 .7 2 (m, 4 , CH2C=), t 4 .2 7 (m, 1,

=CH); mol. wt. 222 (mass spectrum); ir identical with an authentic

3 sam ple.

Alkaline Decomposition of 1-(li-Ditrosoacetylaminomethyl)cyclohexanol

(61) in the Presence of Triethyl Phosphite and Acetone.

A solution of 2.5 g (0.0125 m) of nitrosoamide 6l and 2.08 g (O.OI38 m) of triethyl phosphite in 25 ml of pentane at -10° was treated trLth 2 g (0.037 m) of sodium methoxide in portions during 8 min. After the evolution of nitrogen (j2fo of the theoretical amoijnt in 1 hr) the solid in the mixture -v/as filtered and the filtrate was concentrated on the rotary evaporator. Tihen 1. 5 g (0.026 m) of acetone was added an exo­ thermic reaction took place. After stirring for 1 hr distillation gave two fractions which were analyzed hy vpc (column B, helium flow 75 cc/ m in ).

Fraction 1 (30-l40°/40 mm): columm temp. 115°, A, 2 min, triethyl phosphite; B, 4 min, 0.208 g (l4.8^) of cycloheptanone; C, 7 min, 0.278 g (12.2^) of triethyl phosphate.

Fraction 2 (U0-130°/0.15 mm): column temp. 190°, 7 min, 0.77 g

(26.6%) of cyclohexylidenemethyl diethyl phosphonate (70).

The pure products were isolated hy preparative -ypc on the ahove column. 112

Cycloheptanone and triethyl phosphate were identified hy conparisen

o f i r and vpc retention times with the authentic samples.

Vinyl phosphonate JO: ir (neat); hands at 6.1k p, (C=C), 8.07 p,

( P = 0 ), 9.50 u, 9.75 p, 10.45 p, (P-O-C)j nmr (CCI4 ), t 8.68 (t, J = 7 Hz,

6, -CH3), T 8 .5 4 (m, 6, -CH2-), T 7 .7 6 (m, 2, trans -CHgC^C-P), t 7 . 3O

(m, 2, c is -CH2C=C-P), t 5.9 7 (m, J = 7 Hz, 4, -CH2-CH3), t 4.78 (d, J =

17 Hz, 1, =CH-P); mass spectrum, exact mass measurement 252.1226 (calcd .

value: 252. 1228).

Anal. Calcd for C11H21O3P: C, 5^.9; H, 9.1; P, 15.5.

Found: C, 56 .8; H, 9.5; P, 15.5.

Alkaline Decomposition of 1-(N-Mitrosoacetylaminomethyl)cyclohexanol

(61) in the Presence of Trialkyl Phosphites.

Decomposition in trimethyl phosphite.

A solution of 2.5 6 (0.0125 ci) o f n itro so a m id e 6l and 1.55 g (0.0125 m) of trim ethyl phosphite in 50 ml of pentane at 5° was treated with 1.0

g (0.0185 m) of sodium methoxide in portions during I5 min. The tenpera- ture was maintained he low 7°. After the nitrogen evolution (72^ o f th e

theoretical amount in 15 min) the solid was filtered and washed repeatedly with ether. D istillation of the residue at 40-97°/0.1 mm after the usual work-up afforded 0.4 g of a colorless liquid -v/hich hy vapor phase chroma­ tograph (column B, 190°, helium flovr 66 cc/min) showed only one major

component: 6 min, 0.28 g (lO.8^) of cyclohexylidenemethyl dimethyl phos­ phonate (^), ir (neat), 6. l4 p, (C=C), 8 .O7 p, (P=0), 9.50 p,^ 9.75 h;

nmr (CCI4 ), t 8.54 (m, 6 , -CH2-), T 7.77 (m, 2, t r a n s -CH2C=C-P), t 7 .5 7

(m, 2, c is -CH2C = C -P ), t 6 .5 6 (d, J = 11 Hz, 6 , CH3OP-), t 4.82(d, J = OBtBfcO

4.0 6.0 7 .0 8.0 9.0 1 0 . O T

Figirre 19 - Nmr spectrum, 60 MHz, of 70, in CCI4 u 4

IT Hz, 1, =CH-P); mol. vt. 204 (mass spectrum).

A n al. C alcd f o r CgHirOaP: C, 55-3; H, 8 . 4 ; P , 1 5 .2 .

Pound: C, 53.0; H, 8.5; P, l4.9.

Decomposition in triethyl phosphite.

A solution of 2.5 g (0.0125 Di) of nitrosoamide ^ in 25 ml of pen- tane was added dropwise to a stirred ice cold mixture of 10.4 g (0.0625 m) of triethyl phosphite, 1 g (0.025 m) of sodium hydroxide, 1.5 g of water, and 1 g of Aliquat 536 during 25 min. After the evolution of nitrogen (T2^ of the theoretical amount in 15 min) the mixture was worked up as usual. D istillation of the residue at 55“120°/0.1 mm yielded 1.75 g of products which hy vpc (column b) showed three components at column temperature of 115° (helium flow 8j cc/min): A, 1.8 min, triethyl phos­ phite; B, 5 min, 0.05 S (3-6^0 cycloheptanone; C, 6 min, O.O96 g (4.2/5) trieth y l phosphate and one main conponent at column temperature of 190°

(helium flovr 75 cc/min): D, 6 min, 1.22 g (42%) cyclohexylidenemethyl diethyl phosphonate (jO).

When a 50% solution of sodium hydroxide was added dropvrise to a mix­ ture of nitrosoamide, triethyl phosphite, pentane, and Aliquat 536, followed hy the same wrk-up as ahove, vinyl phosphonate 70 was obtained in 44.2% yield.

Decomposition of 1-(H-Witrosoacetylaminomethyl)cyclohexanol (61) with

Pyrrolidine.

A stirred solution of 8.9 g (0.125 m) of pyrrolidine in I5 ml of hexane at 0° was treated dropwise with a solution of 2.5 g (0.0125 m) of 115 nitrosoamide ^ in 15 ml of hexane duiring 0.5 hr. The mixture tos stirred for two more hours at 10-17°. After the nitrogen evolution stopped (89^ of the theroetical amount) solvents and excess pyrrolidine were removed on the rotary evaporator. The residue was distilled at

62°/0.03 mm to -give 1.95 g of liquid which hy vpc (column l45°, helium flow 156 cc/min) shewed two major components: A, 3» 5 min, 1.19 g (84%)

N-acetyl pyrrolidine (T1); B, 8.5 min, O.5I g (22%) N-( 1-hydroxycyclo- hexylmethyl)pyrrolidine (72). Pure materials were obtained hy prepara­ tive vpc on the ahove column. ...

M-Acetyl pyrrolidine (71) was identified hy the independent syn­ thesis from the reaction of pyrrolidine and acetic anhydride. Infrared spectrum (neat), hands at 6.15 p (C=0); nmr (CCI4 ), t 8 .1 0 (m, 7, -CH3 and -CH2-), T 6.64 (m, 4, -Clig-N-); mass spectrum, m/e II5, 98, 85, and

7 0 .

N-(l-hydroxycyclohexylmethyl)pyarrolidine (72): ir (neat), 2.90 p

(C-OH); nmr (CCI4), T 8 . 5O (m, 6 ), t 8 .2 5 (m, 8 ), t 7 .5 1 (s , 2,

-C (0H)-CH2 -N -), t 7.30 (m, 4, -CH2-N), T 6.65 (s, 1, OH, th is peak exchanged with one drop of D2O); mol. wfc. I83 (mass spectrum).

Anal. Calcd for C11H21WO: C, 72.1; H, 11.6; N, 7.6.

Found: C, 72.7; H, 12.0; N, 7.8.

9 Decomposition of 3-hitroso-l-oxa-3-azaspiro[4,5]decan-2-one (l2) in

D iet hy lam ine.

A 50 ml of freshly distilled diethylamine v/as treated with 5. 52 g

(0.03 m) of nitrosooxazolidone. The reaction i/as very exothermic (54°) n 6

and 950 ml of gas was collected in T min. D istillation on a spinning-

"band colimm yielded I .90 g (56*0^) of cyclohexanecar'boxaldehyde, bp 59°/

12 nnn, and 1.21 g residue. The infrared spectrum and nmr of the product

was identical with an authentic sample.

Alkaline Decomposition of 3-Nitroso-1-oxa-5-azaspiro[4;5]decan-2-one (l2)

in the Presence of Cyclohexene and a Phase Transfer Agent.

A 25'^ solution of sodium hydroxide in water was added dropwise to

a stirred solution of 11.0 g (O.O6 m) of nitrosooxazolidone 12 in 49.2 g (0.6 m) of freshly distilled cyclohexene and T4 g of benzene containing

1.52 g of Aliquat 33^. The theoretical amount of nitrogen >ras collected

in 4 hr. The mixture was worked up as usual. D istillation yielded 4.55 g (43^) of bicyclo[4.1.0]hept-T-ylidenecyclohexane (7^), bp 59° at 0.45 mm (reported bp 68-T0°/0.3 mm).

Alkaline Decomposition of 3-Ditroso-spirorfluorene-9S5~oxazolidin]-2- 17 one (T4) in the Presence of Cyclohexene.

A stirred solution of 2.66 g (O.Ol m) of nitrosooxazolidone and 8.2 g (0.1 m) of cyclohexene in 32 ml of benzene "vras treated "v/ith 0.68 g

(0.01 m) of sodium ethoxide. The mixture was heated at 60-70° for 2 hr.

The evolution of gas did not take place until the temperature reached

40°. The yellow color of the mixture turned into purple and the quanti­ tative amount of nitrogen was collected. The mixture was worked up as usual after it had been cooled to room temperature. The residue (2.06 g) was chromatographed in 200 g of activated 60-200 mesh Silica Gel. The first fraction collected from Skellysolve B-benzene (3:l) gave white 117

fluorescent crystal. Recrystallization from Skellysolve B yielded 0.20

g (l2.T^) pure 9-(l)icyclo[4.1.0]hept-7-ylidine)fluorene (75): mp 126.0- 13 o 126.5° (reported mp 126-127 ); ir (KBr), 6.10 p., 6.20 p,, 8.9O 12.90

p,, 15.54 (j,, 15.70 u; nmr (de-acetone), T 9.21 (m, 2, cyclopropyl), T 8.59

(m, 8, -CHg-), T 2.57-5.16 (m, 8, aromatic); mass spectrum, mol. wt. 258.

Anal. Calcd for C^oHis: 0, 95.0; H, 7.0.

Found: C, 9 5 .1 ) H, 7 .0 .

The fraction collected from chloroform-henzene (l:4) gave 0.470 g

(40,7^) of fluorenone after recrystallization from Skellysolve B. The infrared spectrum and the melting point of the 2,4-dinitrophenylhydra- zine derivative (298°) vere identical with an authentic sample.

Preparation of 5-Acetylamino-2-methyl-2-"butanol (76).

To a solution of 56 g (l m) of potassium hydroxide in 80 ml of water was added 51.8 g (0.246 m) of 4,5,5-trim ethyl-2-oxazolidone under a nitrogen atmosphere. After refluxing for 5 hr the upper organic layer

•vra,s separated from the cooled mixture and dissolved in 80 ml of methanol.

The methanol solution was treated dropwise ’vnth 25 g (0.246 m) of acetic anhydride during 0.5 hr. After 2 hr at reflux the mixture was concen­ trated on a rotary evaporator. The crude product containing acetic anhydride was dissolved in 200 ml of methylene chloride, washed with a saturated sodium hicarhonate solution. After a saturated sodium chloride solution wash and the usual work-up only 2.2 g of brovm o il was obtained.

The aqueous portion was continuously extracted with ether for two days.

After work up 52.1 g of oil was distilled at U5-117°/0.1 mm. Recry­ 1 1 8 stallization from "benzene yielded 2 5 * 9 g (73^) of t^hite crystalline 7 6 ; mp 83. 5-84.5°, i r (%Br), 3 -0 p, (-0H , -M ), 6.1 p- (C=0); nmr (CDCI 3 ) , T

8 .9 0 (d , J = 7 H z, 3 , -CH-CH3 ); T 8 .7 8 ( s , 6 , ( 0 1 3 ) 2 0 ) , T 5 . 8 3 - 6 . 3 3 (m,

2 , -CHCE3 an d OH), T 3 . 00 (m, 1, M ).

Anal. Calcd for C7H15NO2: C, 57*9; H, 10.4.

Found: C, 58.1 ; H, 1 0 .3 .

62 Preparation of Methyl n-Butyl-W-chlorocarhamate (78).

(62) This is the procedure of V. A. Shokol, N. K. Mikhailyuchenko, and G. I . D erkach, J . Gen. Chem., USSR, 3 8 , l4 4 8 ( 1966).

To a stirred mixture of 15. I g (O.l m) of methyl n-hutylcarbamate and 40 ml of vater was added at 10° 15 m l ( 0 .3 3 m) of chlorine hy eva­ poration through a dispenser partially submerged in a dry ice-acetone bath. The reaction was exothermic and the temperature of the reaction 63 mixture was maintained below 15°. The lovrer yellovr layer was separated

( 6 3 ) If the reaction temperature is allowed to go above 80° by a rapid rate of chlorine addition, one obtains a poor yield of the product.

and the aqueous layer was extracted with ether. The combined organic phase was dried over anhydrous potassium carbonate. Ether was removed on a rotary evaporator and the residue \ra.s distilled to give 1 2 . 9 g ( 7 8 ^ ) o f methyl n-butyl-N-chlorocarbamate ( 7 8 ) as a colorless liquid, bp 38-

38°/0.4 mm, ir (neat), 5 .80 p (C=0), 13.30 P-; nmr (CCI 4 ) , t 9 .O3 (m, 3 , 119

-CHs), T 8.14-8.86 (m, 4, -CHg-), t 6.4i (t, J = 7 Hz, 5, -CHz-N-Cly

One o f the peaks s'uperimposed on the singlet from -OCH3), T 6 .2 7 ( s ,

-OCH3).

Anal. Calcd for OgHisClNOs: C, 43.5; H, 7.5; Cl, 21.4.

Found: C, 4 3 .6 ; H, 7 .2 ; C l, 2 0 .2 .

Alkaline Deconposition of Methyl n-Butyl-H-chlorocarhamate (78) in the

Presence of Cyclohexene.

To a stirred solution of 4.l4 g (O.025 m) of chlorocarhamate in

8.2 g (0.1 m) of cyclohexene and 12 g of henzene was treated under nitro­

gen atmosphere 'vrith 1.62 g (O.O3 m) of sodium methoxide in portions

during 5 min. The reaction became very exothermic (temperature rose to 64°). The mixture 'vra.s filtered after it had been cooled to room temperature. D istillation of the filtrate afforded I.70 g (50^) of methyl n-butylcarbamate, bp 50° (0.3 mm).

Alkaline Decomposition of Methyl n-Duty1-N-chlorocarhamate (78).

To a solution of 4.l4 g (0.025 m) of chlorocarhamate in 20 ml of 64 anhydrous ether \ras added sodium methoxide. The reaction -vras very exo-

( 64) The sodium methoxide used in this reaction vras freshly prepared from methanol and sodium sand in xylene.

thermic and the mixture began to reflux. After the mixture cooled down to room temperature the solid was removed by filtering through a pad of

Celite under reduced pressure. The Celite pad was thoroughly rinsed 120 with more ether. The solvent was removed hy distillation at atmospheric pressure, and the residue tos distilled at 44°/0.1 mm to give 1.68 g

(51.3^) of methyl n-hutyIcarhamate. The distillate (l.O g) collected in the dry ice trap shovred two peaks hy ‘V’pc analysis (8' x. ^ / q" column of Carhcwax 20M on Chromosorh W, 100^, helium flow $0 cc/min): A, 1 .5 min, 0.33 g (15%) of dimethyl carbonate; B, 4.0 min, 0.67 g (40^) of hutyl cyanide.

Dimethyl carbonate showed identical infrared spectrum and nmr as the authentic sample.

Butyl cyanide showed ir (neat) hand at 4.5 K; nmr (CCI4), t 8 .9 2

( t , J = 6.5 Hz, 3, -CH3), T 8 .3 3 (m, J = 6 .5 Hz, 2, -CH2- ) , T 7 .7 0 ( t ,

J = 6 .5 Hz, 2, -CHgCN).

In a separate experiment where the reaction was run at 5°; with the rest of the condition identical with that employed ahove, the distribu­ tion of products varied as foUovra: 57.5^ of methyl n-hutylcarhamate,

6.7% of dimethyl carbonate, and 13.3% of hutyl cyanide.