Method of producing thio- dithio- or carbonyl-containing compounds

专利摘要:
Die Erfindung betrifft ein chemisches Verfahren zur Herstellung von Verbindungen der Formel 1 (X = -S-, -S-S-, -CO-, R und R' = unabhängig voneinander H, OH; gegebenenfalls durch mindestens ein OH, Carboxy, C1-6-Alkoxycarbonyl, NH2, Acetylamino, NO2, C1-6-Alkylamino, C1-6-Alkoxy, gegebenenfalls durch mindestens ein OH subst, C5-7-Cycloalkyl und/oder durch Halogen subst. C1-12-Alkyl oder C2-12-Alkenyl; C7-10-Aralkyl; gegebenenfalls durch mindestens ein C1-4-Alkyl, NO2 und/oder Halogen subst. Phenyl oder Naphthyl; 5- oder 6-gliedriger, 1-3 Stickstoffatome enthaltender, gegebenenfalls mit einem Benzolring kondensierter und gegebenenfalls mindestens einen Substituenten enthaltenden Heterocyclus - vorzugsweise 2-Carbometho- xyamino-1H-benzimidazol-5-yl, Pyrrolyl, Indolyl, Imidazolyl, Benzimidazolyl, Pyridyl, Chinolyl, Isochinolyl, 1,2 -, 1,3- oder 1,4-Diazinyl, 1,2,4- oder 1,3,5-Triazinyl, Phthalazinyl oder Chinoxalyl; halogensubst. C1-10-Aralkyl oder durch Reduktion einer Verbindung der Formel II (A = Chlorfulfonyl, R und R1 wie oben) mit einer Schwefelverbindung, die ein S-Atom mit dem Oxydationsgrad (+)4 enthält, der während der Reaktion in den Oxydationsgrad (+)6 überführbar ist oder in saurem Medium zu einer Verbindung mit dem letztgenannten Oxydationsgrad zersetzt werden kann, in Gegenwart von höchstens 0,5 Mol / 1 Mol Ausgangsverbindung der Formel I, vorzugsweise einer katalytischen Menge, elementarem Jod oder einer Verbindung, die in saurem Medium Jodwasserstoff liefert, oder in saurem Medium mit der verwendeten Schwefelverbindung zu Jodwasserstoff reduzierbar ist, wobei die erhaltene Verbindung der Formel I (wenn R1 H und X -S-S-ist) gegebenenfalls in Gegenwart von Cyanidionen mit C1-3-Alkyl-Hal (Hal = Br, CI), in an sich bekannter Weise alkyliert werden kann. Die Verbindungen der Formel I stellen Zwischenprodukte und Stimulantien dar.
公开号:SU1551244A3
申请号:SU853845845
申请日:1985-01-15
公开日:1990-03-15
发明作者:Калдор Иштван；Сас Андраш；Вег Илона；Хайзер Йожеф；Бенедек Ева
申请人:Хиноин Дьедьсер Еш Ведьесети, Термекек Дьяра Рт (Инопредприятие)；
IPC主号:

专利说明:

(21) 3845845 / 23-04
(22) 01/15/85
(31) 154/84
(32) 01/16/84, 27. I 1 .8 (33) HU
(46) 03/15/90. l V Yu
(71) Hinoin Dyedser sert Vekessetn and Termekek Gyra PI (HU)
(72) Istvan K ldor, AH dredge Sag, Ilona Be g, Jojof Hayer and Lna Benedek (Ne;
(53) 547.269.07 (083.8)
(56) Org. Synt Coll, v. 1, p.7. J. Org. Chem, v, 3 /. 1972 h h,
p. 919.
J, March: Advanced Urg.Chem Sec. Ed. 1977, p. 376.
(54) TEETHING TIO-, DITIOOIP and KARONILSODTRmtsikh COMPOUNDS
(57) The invention relates to ketones, in particular, to the obtained ™ thio-, dithio- or carbonyl-containing compounds of formula I R-X-R ,, where X is the i-i-ditio or -C (O) -CI group; R and R, - each H, unsubstituted With, -C-alkoxy-group, straight or branched C, -C-alkyl, C-Cb a1 kenil, unsubstituted or noticed With C, -C-alkyl, halogen OR OR NITPS rrvrrnoi f, pho N Sh1S, - С - al to il 5 2-h a r b to go with him to us about - 1 Н-Оей ичнда ol-5-н .; 9 the second nsgm tg-- is organic synthesis . The goal is to simplify the process and clarify the time of the Target Products. Receiving their redoubt vsgtanmplecheg: United formulas II K - A, where R - vr-gavrgg) - me; L - chlorosupt. - pilt group, group - S (0) R. t .rf, -C (0) -GN (,, where K, is a pumping ng H 1 -, diox.1 systhyde or sulfite or bisulfite of the fritty metal P sms h1 of water and acetic acid in the presence of a catalytic one, but not 0. MO — per 1 mole of the starting compound II}
elemental iodine or yotgnda fi th metal LR 20-80 ° C. The process is carried out with the subsequent isolation of the field product and in the case of the preparation of compound I, where R and K is 2-kpro-ethoxyamino-1H-benimimidazole -5-cp X is dithio-rpvnna, it is treated with a propyl halide in the presence of p-hydroxyl alkali metal to form 2- (methoxycarbonyl) amino-5-prop n-1H-benzimidazole. Preferably, the process is carried out in hrsgw, j or HC1. zp F-LR.
l gak lutp
ffsn-id.
Vn
tBS &
This invention relates to an improved process for the preparation of thio, dithio and carbonyl-containing compounds of general formula I
R-X-R1, where X is dithio- or - (jj-CH -rpynO pa,
R and RT - each hydrogen, nezsegen -, - i, or replaced by. -Appkpk n-group, direct or developed C., C-CЈ-a, - kenil, nezamet ((ki or g; branched C, -C 4 alkyl, C C6-alkeneyl kee meshchennn substituted C, C-alkylsm, ga then gene ohm or nitrogt-ppo;
phenyl,. fnil-g (-akkil-, 2-chrbope 01-SNECh1CH iH nm -, mnadzol-3-yl,
which are used as intermediate products in various4
rGaN1 cheS1 THEM CHIPiE-i.lX t IN VOLUME NEEDLE “
iologichesk-actin reschggv „
The goal of the acquisition is the PHPR PHHL process and the expansion of the acre RGIMOITG, cg of some products.
The goal is achieved by weight l GLS for us of compounds of formula I
K - L,
de R is a frost on decree shn'e –a (section L - chlorosulfonyl a - f ynrci rnynna-S (C) 1ri,
. ha L where R1 - has chazanme 3 degrees,
On 1 - alo g r s
uoxide (ery mon cvj ififium, or alkali metal bisulfite and a mixture of oxen and acetic acid sour, present catalytic, but not more than 0} 5 mol per 1 mole of the original HSR-jHx i I element of electromyotene or gal M1 MF or 20-80 (with the subsequent isolation of the target product and in the case of obtaining a spin I and a le R h K, - -ctr to ethexy-amino-1 H-oen-eimides eol - e-yl and K - digiotrupp, processing then tropypsoloenidrm E npucvTCTFHH was found to be brittle on the metal de semi, 1 w - (t-carboxy tsp) amicho-5- about pchp io-1 Hbm imidazole.
P rn measure In i j che in d1 (n-tg
 DIS LFID
1 g 0.1 m) Ti) XT i ai, g 1 1ri 11
U-TOLUOGGULYUKY UT-, P GYROYUTI I 00 (h L K (.yCFUHl 1 NGLOI „IC) L. K tlO
in a raster of a surgeries, 1 L1 MOLE, iodide, for example, to get rid of a codide (in a minute), E-eaKiu weci takes on a dark color and “Eva color,” to the reaction mixture dB south south slowly through a drop ZSKhtn and zonch1 Geor of Gisup'fita of the trio of pkoi speed, that when RIS-ing and Ps- t of the feed disappeared, the color, which was attributed to the original s of the reaction mixture7. During 1 addition of reactive points CMCI ta rt-hs; about 60 ° C (30 MIU K Theakiir at this temperature is under pressure then TPV pore, i am free of iodine. Io oKOHtciHt H G (I rotated by the action area of 5-mp 5 m / m 5 / m / m / 5 m / m / h). ,, i
P
with
3
L 1
n NOISCHR) 20,4-noio puinopi i idro-01 ng n vc t aiiriHJinii i pt pli h. The reaction mixture is extracted three times but 80 ml of t-rt5 k s am, hexapon phases o (wildfire, viiiti) 1 , 1 p p, IHM tyni- (JH t ohm 1atrsh $ and riuo pi chrr atmo) (Firth, m Dagl. Me pst; rk removed — cacTi pin el at n (, and with a lower IHCM pressure. The product is produced by p / h °, Il iv4-uo-1, the g is indicated in (bologna1, connect the research work on the code 97Х0, T. pi -4J-43r L,
JIMP 4i (U) I,} ohm aaaaaaaa i kie 7 P35 m, d. (Ivf if t i 2i; /, 05 ml. L. (Double i) 2ll; SIE -, ml. (LHHIJKT) Hm
il р mep L. o ic nt -nfs1 ni-d.h yy1 and / i.
Nose tupac F Fi chi (t- j s e difference that 4Meit hpprange ph pH of p-- o voJicv p, f kic i ty i ns-X) dn) th i it 111 -i. x opri hydride ifuJioKff then 10 i n deputy in iii of se и ches - ni. In turn 9). , n, h (,
NMR - h (CiJt. 1, 1 in mat, 1 h kN «7 b / (M D. I N I LF It T
P R & M t 1),. TS 40 IG H f ipasa uf1, h
o i fall - to n n 1, (t -
FROM i44t S, 1L1OPP N (. Trll
НР1ЦРСГ i ЛШМРИЯ-Ot 1 Ig рН 1 Mi
 sf cv ribi K m with l o p i and g ph reannoy oi sm (c i i t hv hchst on e rf h k, (8 “Rotation of mix with i
COP pai NRUYUT TRIKDP software f MJ J lJHP 1 1.
 Peaceful extremist - bt with gpn about, fchakchlo h r about L (2, & 5 grams of Kiri oi i a i about 1 h r ri with Bi xoii f. T i. 1. 1 10 (°, - (i, / / С
H P m e n j Ii i h IMC 3 h i. kag o) s, {- OKI. Not shh. bnn r.ndp i not ul1 i}; t-i
ilociynafOT friK in the make-up artist, the more, then in the quality of the UOP OK substance hch rrn hydride
J.v OJICy 1'FOK t i II I LIP X G 1.
rip 2-carb0 j oi i, cpbp1 about S-cyib sCJ rr 14, Pv i p G 3-thionic with -1y and not all the compounds, test with hexane, ustanschkl in ly p g. the reaction mixture truvdt tri-g h hulu-cure is shaked out | 10 MP Fuel 1 1, GO
-c -I IF or i tvmaT cree reduced d s i i ip 1 iO ° Iyu% h IK i J
5is h:
NMR-N (n 1p-acid acetic acid -d t): 7.8 m. (singlet) 1H; CT-H, 7, ft ppm (singlet) 2H; C4-H, 7.6 ppm. (singlet) 2H; OCH3, 4, Om.d. (singlet) ZN.
Example 5, Preparation of 1-C (methoxy arboyl) -amin on 5-propylthio-1H-benz mnada ol.
36 g obtained according to example 4 0 p-tolyl-N-propnlovogo tnoefnr.
5.5 - (2-carbomethoxyaminobenzimidaeol) -yl disulfide is dissolved in a mixture of 30 g of potassium hydroxide, 25 ml of propyl bromide, 7 g of potassium cyanide, 250 ml of water and 500 ml of acetone. The reaction mixture is stirred at 20-25 ° C for 20 hours. After the addition of 35 g of bicarbonate and trick, the precipitated product is filtered off and washed with 200 ml of 50% v / v, new aqueous acetone and 200 ml of water. 33 g of the title compound are obtained. 75% yield, m.p. 210-212 ° C.
Example 6. Preparation of p-tolyl-1-propenylthioether.25
10 mmol of p-Tolyl-cis-trans-1-propenyl sulfoxide is dissolved in "10 ml of acetic acid, after which 0.2 g of sodium iodide is added. Temperature
Proceed as in example b, with the difference that n-propnl-n-s-sulfoxnd is used as the initial substance and the residue after distillation is divided by fraction. Get 1.4 pumped out in the workpiece connection Output V2Z. T, kip. 78-8 p ° С (266 П njy 1,5450.
W -4 (CIX,
20
: aromatic -7.25 м.ц. (doublet1 2Н- 7 "С ъ. years) 2Н; LCH, 2.85 ml (doublet rH52s3 ppm, (snngchet) OG; CH7CH 1, L5 ppm, (mugglet1 2rf; 1.0 ppm, (doublet) ZN.
PRI me R 9. Obtaining prospect n-tolllallillo-zogo dash ether
PoSiGuH.YUT T 6, G
difference s, that in the kzchgstve and xpdno substance isp. shlyut p-tolyl lips
the mixture is increased to 50 ° C and the reaction of the ox-JQ Fox. Get 0 65 g vsaiab r nro
in the title of connection Yield 39%, T. p.p. 70-73 ° C (2f-, Pa)
The addition of two drops of coicentro-aino and hydrochloric acid is arouse. The liberated iodine is reduced by the continuous addition of a 30% sodium bisulfite solution, and after the disappearance of the iodine color, 3-5 drops of concentrated hydrochloric acid are added to the reaction mixture. The concentrated acid 1a and the sodium bisulfite solution are added separately portion by portion until the iodine is no longer colored when the last portion of hydrochloric acid is added.
The reaction mixture is diluted with 10 ml of water, adjusted to pH 8 and the resulting disulfide is extracted three times with n-hexane ps 15 ml. The combined hexane phases are dried over sodium sulfate and concentrated. 2.1 g of the title compound are obtained. Yield 85%. M.p. 43-45 ° C.
Example. Getting simple methylphenylthioether (thioanisole),
Proceed as in example 6, with the difference that instead of p-tolyl-cis-trans-1-propenyl sulfoxide, methylphenyl sulfoxide and not containing growth of 1, 5710 NMR-H (SPS1E) are used as the starting material: aromatic
35
40
45
7.25 ppm (doublet) 2Hj 7f05 м.ц. (doublet) 2H; 1-5.6 ppm (mul plet) 1H, 6 Hz, H7 Hz; CH2 5.1 ppm. (double doublet) 2H 2JCHA CHj 1 Hz; , 5 m.
(doublet) 2Н 3JCH, j,,
4JCHS, -CH, 0.8 Hz; -CH3 2.3 mp (d years) ZN.
Example 10, Preparation of a simple fequil-3-butenyl thioester.
Proceed as in Example 6, with the difference that phenyl-3-butenylsulfoxide is used as the starting material. 1.2 g of the title compound are obtained. Yield 72%.
, - NMR - H (CD (J13); aromatic 7.5-7.0 M.jfl. (Multiplet) 5H; 15- 5.6 ppm (multiplet) TH; CH-i, 5, 1 ppm (double doublet) 2H; -SCH 3.0 ppm (triplet) 2H; 3JCH ,, H, - 8 Hz; -CHN CH 2.85 ppm (quad) 2H
Example 11 Preparation of simple 1t-tolylbenzene of thiospir.
Acts as E of Example 6, with the exception that as the source
Voronel line after distillation: Fractionated, T. cnp. 18 G, 1.1 g of the compound siphoned in lgolov- 4is are obtained. Yield 88%. ,,
 H (CDC13): aromatic 7.4 ppm (skglet) 5H; - SI, 2.47 ppm (singlet) ZN.
example 8. Getting simple
five
Proceed as in example b, with the difference that n-propnl-p-talk sulfoxnd is used as the starting material and the residue after distillate is fractionated. 1.4 g of the compressed compound prepared in the workpiece are obtained; Exit V2Z. T, kip. 78-8 p ° C (266 Pa), njy 1.5450.
W -4 (CIX,
0
: aromatic -7.25 м.ц. (doublet 1 2H- 7 "Sd (do years) 2H; LCH, 2.85 ml (doublet G11; rH52s3 ppm, (snngchet) OT; CH7CH s 1, l5 ppm; (muggletglet1 2rf; 1.0 ppm, (doublet) ZN.
PRI me R 9. Getting simple n-tolllally-zogo thir ether
PoSiGuH.YUT T 6, G
difference s, that in the kzchgstve and xpdnog- substances isp. shl p-tolyl ltypsulov heading connections Yield 39%, T. p.p. 70-73 ° C (2f-, Pa)
1.5710, NMR —H (SPS1E): aromatic
five
0
five
7.25 ppm (doublet) 2Hj 7f05 м.ц. (doublet) 2H; 1-5.6 ppm (multiplet) 1H, 6 Hz, H7 Hz; CH2 5.1 ppm. (double doublet) 2H 2JCHA CHj 1 Hz; , 5 ppm
(doublet) 2Н 3JCH, j,,
4JCHS, -CH, 0.8 Hz; -CH3 2.3 mp (doublet) ZN.
Example 10, Preparation of a simple fequil-3-butenyl thioester.
It is carried out as in Example 6, with the difference that phenyl-3-butenylsulfoxide is used as the starting material. 1.2 g of the title compound are obtained. Yield 72%.
- NMR - H (CD (J13); aromatic 7.5-7.0 M.jfl. (Multiplet) 5H; 15- 5.6 ppm (multiplet) TH; CH-i, 5.1 m d (double doublet) 2H; -SCH 3.0 ppm (triplet) 2H; 3JCH ,, H, - 8 Hz; -CHHCH 2.85 ppm (quadruplet) 2H.
Example 11 Preparation of simple 1t-tolylbenzene of thiospir.
Acts as E of Example 6, with the exception that as the source
Leaves of yarns are handed i -TOJ ul sbsnd, Get the title compound. Eikhol 88.7%, T pl 43-44 C
NMR H {CDLlj} myeo-displaced-shg aromatic 7.5 h d, () b, d is more subunit of the arches n IHRS. (- /, l d "Tsvoyn and duOlet) ih, -SI, t 9 (b ppm h chenlet) 2b; - SNCh,) h.d., (gin- - t em zb "
lips m fc p 12. Getting just r - i fen yl / y-phenyl i ilono from the keyboard.
I act as an oh, oh, so that, as the original
“Zscheegva apply fenip-b-phenyl-e-gil with u or fok with id. Obtain 1.0 i indicated in the title of the compound, Chocho / g, n / 1, o10i.
I # 1 H (GPCl h). aromatic / 02t 0 ppm multipegj 1 HE; , 5SU ppm Miltipp-) 4H.
Example 13, Preparation of HDOCTOI npoiu l- ri- -Kc..ei ok-nam ebene iids13ol) il thiosiph
T1o payload kai t example 6,
jiT 4J | IOM P O V K 1PCS1 B-- INITIAL O
shyapshch apply i-progil-b - (- KSI b snake yulsiamnobrantsh- and / taz l) P-GUL-G Ch Г Id. When the reaction
 of opus There are extrinsic gscanpm P and neitrlpi onpf and th mgp- (OH /) t pilars of crystals and glas and 1 each (1 ml of water 2yt kazhogo nzat o TovKR g g; ipgchi
hop, 7e
 ABOUT
H
g, pg) 1
 F
(IP and (and,) km n 1.6 h d
ff-ichglrt) 1 k with 1 7 А g Ш1 nt -) 1Н С f М L м с- i 7 t md S; bi g 1; 7b md and ch g g 3f
75 m d (i riple i i i. I i 5 i d ("G PTPLR; 1
 p and m f p (bj ich j j stltaldei a.
100 miol (-e g ohm-e / fen; tayetappr-ida dissolve in 1 DO mt of xugi Igr, K pacrBopv add g
 MMOLE I UDIDR heating 1OCHN
The mixture of those of the PLG, while 1 odd fully diluted 06pd, during the reaction of the iG, was continuously restored with a 30% solution of bicapi. The composition of the TCST 4si ml / Koggs iodine was more than vg H1- (h with 10% g of g of the g and ;;; with sodium in -MPCV mouth with pouring 1 h of pH vw -i i
P and grout on the skin by 2 HI efschom about iris tie ooedn k) g, yuia nag with latifata of Nytri and concentrate, (the matchmakers fractionate g at decayed pressure o / b - from 4 9 S g / ka 3f what in and opon1e connected, Y.og ZN PL ooo Pa ;:
m iKuci; (ns) m i (t-) iplet) W; arcchic ic 7 - /, 0 and l (multiple 1et) jH; - GN - T .65 f-gt (/ 3tet; 24, 3JCH,, UU /

g
g,
S
Q
;
H
i
li pnm b1 p i 5 1 getting n-1 j fucking 1phenone
Proceed to at in the example with the difference that it comes to as a result of the e-BaBa of the Ј-bro-th elais apde dreda primelgs br and rr J; Ofr sawing tone. When working, the rgaktz yum and SMIRGI are responsible for what is described / that i rhymer 1 h oi 1 hakci) 1. the ancestor of the os was given with smrh h 0 ml of water :-) EJM
rinsed and washed, and n 2 ° m. I get l, i y 3Pior header g OP / NRRC n, 1 pl / F 9 °
NMR 1 C (I) r i 3) i t ft, 3 mp d JT) 2H; I I ppm rx, f 2fl- -Hz; i t ni
GT g N G p 1 f- хц i j
ri I t ip hm but 1 1
  J-t; a,
 u g (10 MMC i). orang i
I m pg, h °
ON MMO and h or 11 and three U f t ir b about and p - t 1 n 11 -f h (i ° s
(REPEAT () YAGYu7 2
C / KCGGy g) I p g | Qp-yLnr r
°, 1 OIII tl -rnch
vp me i, i j t n
IBO IT 1 G 1 I 1C L
t Ml u ОЬ рТГЬ V j (. I
ILdi lI.PK tII th
tvayug add leii iw ЗГ I him pacTj pi big / lofita sodium, Temperature re rt f tf o r ° ine., 0 MI h o r a t s up to 70 C P oo h h sh r a1 c - ka i rda 6iit is g e f- g g yusch | Gb1, and h 11 is, it is limited to 20 m t h jiv it n about ™ -tii “OL con c) M i C - from CTBtjDa i i d irox 1Д ija ibj v ayug 3f-c-рnir pl - 1, F i ex IRG i with i-ri-tapes otfil i i i im -. The PREMIR of the Trinity ps 20-lg-r-x hrg pts is plotted on the low frequencies with that C Thu Cht1, a depth of 9 cm, i m c; g with
G PI TOTibitl 5H I IT-1
91
The mixture was chloroform 9: 1 with acetic acid, RЈ the value of the title compound was 0.62. By concentrating the eluate, the desired product is obtained in a yield of 40%. M.p. 225-230 ° C (decomposition).
(d e): NH 12.65 ppm (singlet) 1Hj aromatic 7.6- 7.1 ppm (multiplet) 7H; -0-CH3 3.75 ppm (singlet) ZN; -CHj 2.3 ppm (singlet) ZN.
II p & me r 17. A 2.2 g Chlorine p-chlorobenzenesulfonic acid hydride is dissolved in 400 ml of 99% acetic acid and 2 g of iodine is added to the resulting solution. After that, through the reaction with. Pass gaseous sulfur dioxide. such a speed



tyu, so that ouryn color iodine dog time disappeared. During the passage of gas, the temperature of the mixture slowly rises to 80 ° C.
After ts go, round coloring
,
at the same time, the hempere-rew isn’t occurring.
c, to a mixture of dobopp yug 200 ml of water, and then - 20P mp chplo:. The cyclohexane flocculate is separated, and the water is twice subjected to cnclohexanc buildup in 50 ml portions. The cyclohexane extracts are combined, dried over sodium sulfate, filtered and evaporated in vacuo. The residue after distillation is calculated by di (p-chlorophenyl) disuda | id. V-hol 264 g (92%), so pl. 70-72 ° g ,, 1H-NMR: 7.2-7.5 m.
II pnmop 1 8. 15.8 g (O, 1 mol) chlorine hydride of 2-labeled synganol sulfate and 2 g of sodium iodide are dissolved in 60 ml of acetic acid, after which 40% - aqueous solution of bisulfite
Squash at such a rate as to color, dignity .. Hexap phases are combined,
As the continuously forming iodine disappeared all the time. At the same time, the temperature of the mixture rises to 70 ° C. After the color: iodine ceases to appear as the reaction progresses, 00 ml of hexane is added to the reaction mixture and then adjusted with 10% sodium carbonate solution. The phases are separated. The hexane phase is shaken twice in a separating funnel with 50 ml of water and dried over anhydrous sodium sulfate. After that, the hexane solution is separated from the drying agent by decantation and evaporated.
and the solvent is removed. The product is purified using a chromium-gravure column (for gel (; 4, eluent:
/,
50
with v / v, pressure - Oag g p then l and forehead n zil t io ether
55
Hexal - LtJA
The yield is 1.82 (85%).
The results of the analysis are the same as in example 1 1.
Thus, the proposed CGNP allows one to obtain different compound efficiency ranges — sulfides, disulfides and ketones, known methods for each of which differ in duration, low yields and low selective 6
1244
0
five
10 Output 2-methoxynethnig dignd 83Ј.
 f (CC14 / TMS): 3.53 (t, 4H); 3.30 (s, bH); 2.80 (t. 4H).
Elemental analysis data, Z: С 48 (48); H 4.2 (9.3); S 21.1 (21.3).
II Example 19: 2.44 g of p-Nntro-broth tophenone (p-nitrophenyl bromo-ketone) is dissolved in 10 ml of 99% acetic acid and 0.1 g of sodium iodide is added to the reaction mixture. Thereafter, sulfur dioxide is blown into the reaction mixture at 30-35 ° C, so that the continuous color of the nodd formed during the reaction period. If the color node after the termination of the flow stream S04 is greater
0
five
0
five
0
when the tie appears, the reaction mixture is diluted with 30 ml of water; the precipitated crystals are filtered out.
Yield 1.5 g rn Introacetophenone. (91%).
The results of the analysis are the same as in Example 15.
II p p Uer 2P, 2.3 g p-toluene-bene sulfoxinda j .iCi nop «wi i; 0 mg of acetic acid, P of the reaction mixture are added with 2 ml of hydrochloric acid and 010 and .eM; ie, the reaction is increased to 70 ° C. Thereafter, the dioxide is serious; rinse through the reaction mixture, so that the cepe- croc to the skrychka zchananchate 1 o:; ode disappeared not rijir-pt-iBHo. B.ln after imbalance of the gas flow iodine pain - about pochtochots, then tsm. And the treatment is reduced to 20 C and the mixture with slop; A 10% solution of sodium hydroxide and sodium hydroxide is adjusted to a pH of 8.
The product is subjected to three-time extraction with hexane, and cr. 10 ml of gossane is used once. The hexapic phases are combined,
and the solvent is removed. The product is purified using a chromium-gravure column (for gel (; 4, eluent:
/,
0
with v / v, pressure - OAG), r p then l and forehead n zil t and o ether;
five
Hexal - LtJA
The yield is 1.82 (85%).
The results of the analysis are the same as in example 1 1.
Thus, the proposed CPSP if allows to obtain different compounds of compounds - sulphides, disulfides and ketones, known methods for each of which differ in duration, low yields and low selective effects.
Whose, unsuitable ycnosf-tm;, and about - m-lngennogo scale and go in general, 1 their application is complicated. According to the proposed method, new compounds (for example, a compound according to an example) are better than the Torojone, and this broadens the range of products obtained;
d о р м / л а and з о Э j г г - и и and

权利要求:
Claims (2)
[1]
1. A method for producing pito-ilt carboxyl-containing compounds of general formula I
R - X-R
t
DV X TIO-, DCH7IOOIIAI -1
-GN -ru-t; o
na;
to R e - each hydrogen i placed or replaced (by a group, direct inn is shredded with C, C4 C5Chyl, alkenyl, not seen or hesitant C, –C pykyl i, halo- 25 tons of en or. –I "Tro gsuppie fenip, cbpfiHr - C - C - alip -, - Carbometo C - h - g - 1H - 1enee11mchda-) goganschlenyom. ; .- h and-tH about 5shih forms
iyjiii t1
R as
rte R HMPGT data
p - chlorosulfonite GRU PM, pvn-
f)
about
five
h - Sfo) Wh-L-CH- g b b Pa
where R, goteg u azanchyr -Maiic fip
Ht3 - hapogr,
o1 / ica- tagg- that, in order to simplify the process and decompose the sorts of the sortinent, the protrusion is carried out by two sulfur or sulphite, or alkaline bisulfate of meg & g in the water mixture in the cis and ygs, but no more than CS5 mol 1 mol of the starting compound rls of evil meninged iodine or y-edid chips cho-- mgtalla at 20-80 s followed by the release of the ridiculous product f in c f to get the compound (e JK I where R and R (- 2 carbotoxiamini - L-yuzimida-dazol-Z-l, l AHi oipynna, its C is working horn and / halogen & ny in the presence of hydroxide LfTetanus metal.r € s to give 2- (metoksikasbonchl) but amino-5-benzyl-1H proliltio schaeola them,
[2]
2. The method according to claim i and h 4 and 4, and that the process of wire 1 is preserved whether it is lit up with acid
and 7
t and
ri o
G Ii
ifc hch 86 i rc X - ditiogr a; 7 М S4 мри X - chosd d gcho i farbe ni / nvnn

类似技术:

---

公开号 | 公开日 | 专利标题

---

SU1551244A3|1990-03-15|Method of producing thio- dithio- or carbonyl-containing compounds

---

ES2279559T3|2007-08-16|SYNTHESIS PROCEDURE AND COMPOSITIONS OF BCH-189 AND RELATED COMPOUNDS.

---

AP1709A|2007-02-27|Ethanolate of azithromycin, process for manufacure, and pharmaceutical compositions thereof.

---

CZ350596A3|1997-09-17|PROCESS FOR PREPARING N-£3-|PHENYL|-N-ETHYLACETAMIDE

---

US2628982A|1953-02-17|Bis | sulfone

---

DE69916030T2|2004-08-05|METHOD FOR PRODUCING OPTICALLY ACTIVE THREO-3-AMINO-1,2-EPOXY COMPOUNDS

---

US4604240A|1986-08-05|Homobrassinolide, and its production and use

---

JP3453188B2|2003-10-06|Method for producing oleanolic acid derivative

---

US2534562A|1950-12-19|Method of preparing zinc selenide

---

US4255563A|1981-03-10|Process for preparing anthocyans from corresponding flavonoid glycosides

---

Bravo et al.1987|Synthesis of the |-5-hydroxy-decan-4-olide | and of the |-decan-4-olide from a chiral sulphoxide

---

HU198065B|1989-07-28|New process for producing beta-lactam derivatives

---

US4734508A|1988-03-29|Process and intermediates for preparing 4-substituted proline derivatives

---

US6340752B1|2002-01-22|Deprotection and recrystallization processes

---

CA3073359A1|2019-03-07|Process for the preparation of arylsulfonylpropenenitriles by photocatalytic reactions

---

DE19631542C1|1997-08-28|3-Sulphatoxy-oestra-tri:ene alkali metal salt production

---

US2190167A|1940-02-13|Process for production of ascorbic acid

---

US2542796A|1951-02-20|N-ethylpiperidine salt of penicilling

---

US3684674A|1972-08-15|Process for preparing 18-cyano-pregnane compounds

---

DE2348616C3|1978-07-27|Process for the production of optically active tryptophan

---

US3728333A|1973-04-17|Method of obtaining monohydrate of sodium salt of 6-|-penicillanic acid

---

IE862218L|1987-03-06|Penicillanic acid derivatives

---

CN112142631A|2020-12-29|Synthesis process of high-purity sodium polydithio-dipropyl sulfonate

---

CN110028542A|2019-07-19|The clean preparation method of canrenone

---

SU1523581A1|1989-11-23|Method of processing sulfide lead concentrates

同族专利:

---

公开号 | 公开日

---

HUT40404A|1986-12-28|

---

JPS6133131A|1986-02-17|

---

EP0150026A3|1986-02-12|

---

EP0150026A2|1985-07-31|

---

US4656290A|1987-04-07|

---

HU192973B|1987-08-28|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US4069259A|1976-10-19|1978-01-17|Allied Chemical Corporation|Process for preparing organic disulfides|

---

DE3216126A1|1982-04-30|1983-11-03|Cassella Ag, 6000 Frankfurt|METHOD FOR PRODUCING DISULFIDES|DE3633968A1|1986-10-06|1988-04-07|Hoechst Ag|CHIRAL ARYL-2,3-EPOXYALKYL ETHER AND ITS RELATED THIO COMPOUNDS AND THEIR USE AS DOPE IN LIQUID CRYSTAL PHASES|

---

FR2647117A1|1989-05-18|1990-11-23|Elf France|

---

KR100654208B1|2005-12-05|2006-12-06|주식회사 제이엠씨|Process for preparation of aromatic disulfide|

---

JP5482233B2|2010-01-27|2014-05-07|宇部興産株式会社|Method for producing diaryl disulfide compound|

---

JP6269300B2|2014-05-01|2018-01-31|国立大学法人大阪大学|Catalyst for deoxygenation of sulfoxide, and method for producing sulfide using the deoxygenation catalyst|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

HU84154A|HU192973B|1984-01-16|1984-01-16|New process for reducing sulfochlorides, sulfoxides and alpha-halogenocarbonyl compounds for producing dithio-, thio- or carbonyl compounds|

---