SU519418A1 - The method of obtaining derivatives of 2-oxa3-azabicyclo [3,1,0 / hexene-3 - Google Patents

Description

I

This invention relates to the production of new derivatives of 2-oxa-i-3-azabicyclo-GZ, 1.0Z-hexene-3, which can be used as intermediates, for example, in the synthesis of h klopropanov.

 According to the proposed method of producing new 2-oxa-3-azaba-derivatives; cyclo-GZ, 1.0 hexene-3 of the general formula (1)

NZS.

where R. is methyl, phenyl, substituted a; if necessary, chlorine, bromine nit. ; rogroup

R - is hydrogen in methyl p carbomethoxl „a compound of the general formula (П) НзС,

where RJ is defined above, G is the interaction with the compound, the keys of the general formula (1H)

R CCCIU N01U

and where R has the above meanings, | and triethylamine in an organic solvent, with the selection of the target product from a known technique.

i The process is carried out at the precipitation of the n-ap10 to up to (-1O) - (-15) C. Ether is used as a solvent.

Derivatives of 2-oxa 3-azobitsinko-- Z. J ,. -Hexene-3 is synthesized by the following schemse:

it.c

15

agS-to odm | with.

, fgw

: flH-XiY where is methyl, the values of Sj are trace5 and they are:;

Compound

f Vl 1. j. rf :,,

i- -BiC,

. g t g 5 f

", E, 41

to p & CTBOpy xorida gsch; 1G EMC; H ": J® W-H; IT lOf) ™ 2OO% -BMi-i excess 1.3 I;, 3-f; flSi;: -.; - eT y. (S; aKJ oirspoaesa E avg orgashgches-. :: oro pacTsopsreHSj for example cyj ;: :; zfara, f l / more, it is located in 3S C-IO) - (-iSlb.j | iu 4 -;: /; 0: Has -F-o MSSH with ay EMBSyyyashsh iriy | 15 ud sguzo-r akv 1 Ohigar: a1 about the concustatious tr; -1 etchzimyka. Obra g yosto nrnr this M -: -ci,: acb Bzagchmodeystoyet s. S3-UMXA ;:) npoH & ROM, j giving soaaa: yena 111-S; Os "; :: ok Bypassed by xaopi-sjapuTa of traethylaalkum,;: o.-orya nvakShch esea jse is soluble in efi-I, j.: Ij о / фдлт а®menter, 5 several times, proadsВ1: 1гг c; .v: LK , i sfaroMd and an associated epar: .i-; ii,; L jiucfficp myarzzvalet in a vacuum, Ogattozh;: ..; a, and (C1 th Shaait as l®trolledSS

   - .; ,; about .--,-

:; i.- :. /.

 C /; r-j:; oeiiii.s 1g 1Seech1: EJL Compound prnny-ki Ha based on the data of an elementary analogue and GSR spectra. The presence of one-proton; ChOD; in the area of m, d. in 1:; ye; 1tr x BSvk Sentseyr-ozannmkh connection ™ I

yi indicates zga structure X bab-trimethyl-)

i 2-.c: xa-3 -aaabieEIKls -.- 3,

HexCoGoSyGtGg, exit n yanzaz amentago | a.iJfijhHsa obtained compounds like table

P r and l er 1. To pivcTBopy 1,4-3,6. Phenylhydroxamic acid chloride and an equimolar amount: "Lethyl ester 2j ZEZ-trimethylcycloprophencarboxylic acid {In the case of tetramethylcyclopropene: take a two-fold excess of the latter) in 10-20 ml of dry ester for 4 O-bOmin with affective mixing and n-tereteramidine-terephthalate; round (--Y) - (15) With a solution of j 1. z4-3,, 6 mmol of triethylamine in 20-23 ml | dry efnra. Mixed stirring continues at 20 C Is-5-2.-O hour (4-6 hours in a ring of tetrame j (4-6 h)) triethyl precipitate | Ammoki x Orida otfshchltrovshayut and gfomyvyut bitches ether. The solution was evaporated and the crystalline adductX was isolated. After derekrist lizatsin from petral ether (40-70) chromatographgs IM

t. gsh 5 5.5-56.0 C.

KM in, individual

: EXAMPLE; p 2. To a solution of 2 ,, 8 g (12 L Lmol) chloride h - bpg4Hg - phenylgyro: Esamic acid and 2 g {24 myol) 153 (, 3-trime Gylts1 "1propropene in SO -4O ml of dry ester pr) - i lSfc for 4-5 minutes from solution 12: -loop & triethylamine B 5-10 mi dry ether. The precipitate of triethylain hydrochloride is filtered off, carried by YediOO times (with dry ether, distillation solution and evaporated from the hydrochloric acid solution. (4O-7Q). 6,6-trimethyl-2-oxv - 3 - azabE11iklo - fS, i, Ol-hexene-3, as well as electrical 4-dose anapis are given in -raSisisae, i

Output .

Nazaayuge

; 11rods "reading-table.

Ele mentarn, 1st composition

Found | .., 1 out

p-, ™ ..-- 4 rrugg

156; 6-TRIMvTED-4 (y--

ioq .65.0-; 1lof8 imn} 2; -OKca. 3-aeabiniklo- Z. laOj-hexene 3

1,6,6 -Trame-tsh-4-1 i-nitrof-aEEZ-) -2 - oxa - 3 - azab jiklo-1 .3 1 Dl - rsK

I S 5dt ,, f-L .CiOt cl

I

M

IMZ C ,, And, Nao,

n 1J in J 6 Gy; 1shshsh1--1 -i-iitrophenip)) JSA - 3-azabicycic-, 1.6 E, 6-TrimethESH-4- (ynitrophenyl) - 2 OKca-3-aeabicyclo-3 , 1 O sen-3 15b8b-TRIMVTIL-4-f8ShP 5-karbomvtoksi-2-oksa 3-aabicytso lo-1 Zd 1.0 1,0 "hexagg 3 1b5b-Trametsh.4 th -nitrophenyl-5 -k: arbometozheto- 2 oksa - -zabitsikpo-13, 1 ol-reitteeH- 3 i 5b8b- Trim8Tyl-4-41 Chlorfv1shg1-5- karbomvtoksy ™ 2 --- oksv 3 azabi iK l 3,1 jOl r6KceiJ 3

. 5.82

H

5.66

11.50

11.70

4.75 4.74 3.0S | C, ISfi s% | 2, sa C4 .. 69 ,; 48 69.03 "f G8 69.06 CisH, s% G, 59.08 el 181 5.27 9.52 9.53 e, q, 1mp 61.40 61D 6

Short Table