GB2137193A - Chlorosulphonic Acid Esters - Google Patents
Chlorosulphonic Acid Esters Download PDFInfo
- Publication number
- GB2137193A GB2137193A GB08308615A GB8308615A GB2137193A GB 2137193 A GB2137193 A GB 2137193A GB 08308615 A GB08308615 A GB 08308615A GB 8308615 A GB8308615 A GB 8308615A GB 2137193 A GB2137193 A GB 2137193A
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- United Kingdom
- Prior art keywords
- formula
- chlorosulfate
- compound
- reaction
- halogen
- Prior art date
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- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical class OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- -1 alkylene di-esters Chemical class 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- PJBIHXWYDMFGCV-UHFFFAOYSA-N chloro(chlorosulfonyloxy)methane Chemical compound ClCOS(Cl)(=O)=O PJBIHXWYDMFGCV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 150000002367 halogens Chemical group 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000543 intermediate Substances 0.000 claims description 8
- XTHPWXDJESJLNJ-UHFFFAOYSA-M chlorosulfate Chemical compound [O-]S(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-M 0.000 claims description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- UBQPMTQKJYOWDV-UHFFFAOYSA-N bromo(chlorosulfonyloxy)methane Chemical compound ClS(=O)(=O)OCBr UBQPMTQKJYOWDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- KNVLCWQKYHCADB-UHFFFAOYSA-N chlorosulfonyloxymethane Chemical compound COS(Cl)(=O)=O KNVLCWQKYHCADB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RYAGQMSEMGVLGY-UHFFFAOYSA-N 1-chloro-1-iodoethane Chemical compound CC(Cl)I RYAGQMSEMGVLGY-UHFFFAOYSA-N 0.000 description 1
- NJZSDKXVYSAVBN-UHFFFAOYSA-N ClS(=O)(=O)O.S(=O)(=O)(OCCl)Cl Chemical compound ClS(=O)(=O)O.S(=O)(=O)(OCCl)Cl NJZSDKXVYSAVBN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NKZMPZCWBSWAOX-IBTYICNHSA-M Sulbactam sodium Chemical compound [Na+].O=S1(=O)C(C)(C)[C@H](C([O-])=O)N2C(=O)C[C@H]21 NKZMPZCWBSWAOX-IBTYICNHSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- TUDWMIUPYRKEFN-UHFFFAOYSA-N bromoiodomethane Chemical compound BrCI TUDWMIUPYRKEFN-UHFFFAOYSA-N 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- PJGJQVRXEUVAFT-UHFFFAOYSA-N chloroiodomethane Chemical compound ClCI PJGJQVRXEUVAFT-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- FKENQMMABCRJMK-RITPCOANSA-N sulbactam Chemical compound O=S1(=O)C(C)(C)[C@H](C(O)=O)N2C(=O)C[C@H]21 FKENQMMABCRJMK-RITPCOANSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D499/00—Heterocyclic compounds containing 4-thia-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. penicillins, penems; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/26—Halogenosulfates, i.e. monoesters of halogenosulfuric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Novel compounds of the formula <IMAGE> in which X is halogen or <IMAGE> and R1 and R2 are hydrogen or alkyl are useful in the preparation of alpha -haloalkyl esters or alkylene di-esters of carboxylic acids, e.g. 1,1-dioxopenicillanic acid esters.
Description
SPECIFICATION
Chemical Compounds
The present invention relates to new important intermediates, e.g. for use in the preparation of ahaloalkyl esters or alkylene di-esters of carboxylic acids. The invention also relates to methods for the preparation of these new intermediates, such methods also being useful in the preparation of compounds of similar structure.
The new intermediates are represented by formula I
in which formula X is halogen, e.g. chlorine or bromine, or another good leaving group, e.g.
and R1 and R2 are hydrogen or lower alkyl.
The compound of formula I in which R, and R2 are both hydrogen and X stands for chlorine is known from Ber. 60, 2288 (1927).
The compounds of formula I are very effective reagents for introducing the
group, e.g. when preparing a-haloalkyl esters of formula II
in which formula R1 and R2 have the above meanings, X is halogen, and R indicates an organic residue, by reacting a salt of a carboxylic acid R--COOH with a compound of formula I (X=halogen), thus obtaining the compound of formula II in better yields and of higher purity than when using the usual method of reacting a dihaloalkane with a salt of a carboxylic acid.
Depending on the reactivity of the leaving group X as compared with the reactivity of the chlorosulphonyloxy group as leaving group, it is possible to produce a compound of formula Ila
in which R, R1 and R2 have the above meanings, and X' stands for X or for
i.e. if X has less or the same ractivity as
The compounds of formula I are esters of chlorosulphonic acid. As a-halo-substituted alcohols do not exist, it is not possible to prepare these compounds by the standard method of reacting sulfuryl chloride with such alcohol.
According to the present invention, the compounds of formula I may be prepared by reacting chlorosulfonic acid with a compound of formula Ill
in which formula R1, R2 and X have the above meanings, and Y stands for a better leaving group than X. In case Y has the same reactivity as X, the reaction will give bis(chlorosulphate)alkane. The reaction is performed with or without a solvent present depending upon the reactants in questions, and at a temperature between --200C and 1000C.
In a second method of the invention, the compounds of formula I in which X stands for halogen, in particular chlorine, may be prepared by a photochemical halogenation of alkyl chlorosulfates of the formula V
in which R1 and R2 are as above, if desired, dissolved in a suitable, to the reaction inert organic solvent, such as carbon tetrachloride, into which the desired halogen is introduced with simultaneous irradiation of the solution. When the reaction has taken place, the product is isolated e.g. by distillation.
If in formula I R1=R2=H and
this compound, bis(chlorosulphate)methane, may be prepared by a reaction between chloromethyl chlorosulfate and sulphur trioxide. The compound is obtained from the reaction mixture by distillation at low pressure.
The present invention will be further illustrated by the following examples which shall not be considered limiting the scope of the invention.
EXAMPE 1
Chloromethyl Chlorosulfate
Chlorosulfonic acid (200 ml, 349 g, 3 mol) and bromochloromethane (100 ml, 194 g, 1.5 mol) were mixed and refluxed for 3 hours. A large amount of bromine was generated. The mixture was cooled and poured into ice, and methylene chloride (100 ml) was added. The organic phase was washed with water (100 ml), dried with magnesium sulfate and solvent was removed in vacuo along with bromine. The residue (93.7 g) was distilled in vacuo, and chloromethyl chlorosulfate was collected at 45-500C/9-1 0 mm Hg.
EXAMPLE 2
Chloromethyl Chlorosulfate
A solution of chlorosulfonic acid (58.3 g, 33.3 ml, 0.5 mol) was added during 1/2 hour from a dropping funnel to an ice-cold solution of chloroiodomethane (44.1 g, 18.3 ml, 0.25 mol) in methylene chloride (100 ml). After stirring for another hour with ice cooling, the mixture was poured into ice. The organic phase was washed with water, decolourised with sodium thiosulfate and dried with magnesium sulfate. The almost colourless organic phase was concentrated in vacuo (22.4 g). Distillation in vacuo gave chloromethyl chlorosulfate at 42--450C/9 mmHg.
EXAMPLE 3
Chloromethyl Chlorosulfate
A flask containing methyl chlorosulfate (10 ml) was placed in a water bath at room temperature.
Chlorine was bubbled through the liquid which was irradiated with ultraviolet light from a high pressure lamp. After 3 hours, an NMR-spectrum indicated a 70% conversion to chloromethyl chlorosulfate. The mixture was cooled in ice and methanol (4.6 ml) was added in order to destroy unreacted methyl chlorosulfate. Distillation in vacuo gave pure chloromethyl chlorosulfate, b.p.
550C/20 mmHg.
EXAMPLE 4 a-Chloroethyl Chlorosulfate
A reaction flask containing ethyl chiorosulfate (15 ml) was placed in water bath at room temperature and irradiated with UV-light from a high pressure lamp while chlorine was bubbled through the liquid. The reaction was followed by
NMR-spectroscopy and the chlorination was stopped when all the starting material was used up. The system was flushed with nitrogen and the product (a mixture of chlorination products) was distilled in vacuo through a Vigreux column. The fraction with boiling point 49-51 OC/10 mmHg was a-chloroethyl chlorosulfate.
The IR-spectrum (CH2CI2) showed strong bands at 1415, 1192, 900 and 600 cm-'. The NMRspectrum (CDCI3) showed peaks at b=1.97 (d,
J=5.9 Hz, 3H), and 6.47 (q, J=5.9 Hz, 1 H) ppm.
EXAMPLE 5 a-Chloroethyl Chlorosulfate
Chlorosulfonic acid (10 ml) was slowly added to an ice-cold stirred solution of 1-chloro-1
iodoethane (9.3 ml) in methylene chloride
(50 ml). After stirring for another hour with icecooling, the dark red mixture was poured on ice.
The aqueous phase was extracted with methylene chloride and the combined organic phases were washed with aqueous sodium bicarbonate and aqueous sodium thiosulfate. The almost colourless organic phase was dried and concentrated in vacuo. Distillation in vacuo gave a-chloroethyl chlorosulfate identical with the
product obtained in Example 4).
EXAMPLE 6
Bromomethyl Chlorosulfate
Chlorosulfonic acid (52.4 g, 30 ml, 0.45 mol) was in four equal amounts with 1/2 hour intervals
added to an ice-cold stirred solution of bromoiodo
methane (22.1 g, 7.55 ml, 0.1 mol) in tetrachloro
methane (100 ml). After stirring for another 1/2
hour the mixture was poured on ice and filtrated.
The organic phase was washed with water,
decolourised with sodium thiosulfate and dried
with magnesium sulfate. Distillation in vacuo gave
bromomethyl chlorosulfate at 62-660C/12 mmHg.
NMR'H: 6.00 (CDCl3).
Calculated for CH2BrCIO3S: C: 5.73, H: 0.96,
S: 15.31.
Found: C: 5.88, H: 0.96, S: 15.63.
EXAMPLE 7
Bis(chlorosulfate)methane
Chloromethyl chlorosulfate (62.5 g, 40 ml, 395 mmol) and sulfurtrioxide (38.3 g, 478 mmol) were mixed at room temperature. The mixture was after 20 days poured into ice, and methylene chloride (100 ml) was added. The organic phase was washed with water (100 ml), dried with magnesium sulfate and solvent was removed in vacuo. The residue was distilled in vacuo 10-11 mmHg, whereby chloromethyl chlorosulfate (starting material) was obtained at 41--45 OC and bis(chlorosulfate)methane at 1 02--1 05 0 C/8--1 0 mmHg.
NMR'H: 6.15 (CCI4).
Calculated for CH2(OSO2CI)2: C: 4.90, H: 0.82,
S: 26.17, Cl: 28.94.
Found: C: 5.12, H: 0.86, S: 25.79, CI: 28.79.
EXAMPLE 8
Bis(chlorosulfate)methane
Chlorosulfonic acid (74.6 ml) was added slowly
to a stirred ice-cold solution of methylene iodide,
(15 ml) in methylene chloride (100 ml). After
stirring for a further 30 minutes, the reaction
mixture was poured on ice. The organic phase
was separated, washed with aqueous sodium
bicarbonate and sodium thiosulfate, and dried
over magnesium sulfate. The solvent was
removed by distillation at atmospheric pressure, and the residue was distilled in vacuo.
Bis(chlorosulfate)methane distilled at 108 1 100C/10 mmHg.
EXAMPLE 9 Bis(1,1 -dioxopenicillanate)methane
Water (150 ml) methylene chloride (200 ml),
tetrabutylammonium-hydrogen sulfate (1.0 g),
sodium hydrogen-carbonate (13.4 g, 160 mmol)
and penicillanic acid-1,1-dioxide (11.65 g, 50
mmol) was charged and cooled to 20C.
Bis(chlorosulfate)methane (5 g,21 mmol) in
methylene chloride (30 ml) was added during 1/2
hour. The mixture was allowed to react 1 hour at
20C and 1 hour at room temperature. The
reaction mixture was separated, and the water
phase was extracted with methylene chloride '(100 ml). The combined methylene chloride phases were dried with MgSO4 and filtered.
Isopropanol was added, and methylene chloride was evaporated in vacuo while bis(1 ,1- dioxopenicillanate)methane crystallizes. Filtration and drying gave a pure product, the NMR of which was identical with that of an authentic sampie, confer U.S. patent No. 4,309,347.
EXAMPLE 10 a-Chloroethyl 1,1 -Dioxopenicillanate The temperature of a mixture of sodium 1,1
dioxopenicillanate (8.85 g), water (35 ml),
methylene chloride (35 ml), sodium bicarbonate
(11.7 g) and tetrabutylammonium hydrogen
sulfate (1.2 g) was adjusted to 20-220C.
a-Chloroethyl chlorosulfate (7.17 g) was added
during 1 5 minutes to the stirred rriixture. After
stirring for a further 30 minutes sodium iodide
(5 g) was added followed by sodium thiosulfate to
decolourize the mixture. The organic phase was
separated, dried and concentrated in vacuo. Ethyl
acetate was added, and the remaining methylene
chloride was removed in vacuo. The product (a
mixture of the two diastereomeric forms)
crystallized from ethyl acetate.
The NMR-spectrum (CDCl3) showed both
diastereomeric forms (in the foilowing called A
and B): Form A showed peaks at os=1.45 .45(s, 3H), 1.65 (s, 3H), 1.87 (d, J=5.5 Hz, 3H), 3.49 (d, J=4 Hz, 2H), 4.40 (s, 1 H)., 4.67 (t, J=4 Hz, 1 H) and 6.59
(q, J=5.5, 1 H) ppm.
Form B showed peaks at =1 8=1.48 3H), 65 (s, 3H-), 1.87 (d, J=5.5 Hz, 3H), 3.49 (d, J=4 Hz, 2H), 4.42 (s, 1H), 4.67 (t, J=4 Hz, 1 H), and 6.63
(q, J=5.5 Hz, 1 H) ppm.
EXAMPLE 11 Bromomethyl 1,1 -Dioxopenicillante
This compound was prepared as described for a-chloroethyl 1,1-dioxopenicillanate by
substituting bromomethyl chlorosulfate for cr-chloroethyl chlorosulfate.
The NMR-spectrum (CDCl3) showed peaks at S=1.50 (s, 3H), 1.63 (s, 3H), 3.50 (d, J=4 Hz, 2H), 4.45 (s, 1 H), 4.67 (t, J=4 Hz, 1 H), 5.76 (d, J=5 Hz,1 H), and 6.08 (d, J=5 Hz, 1 H) ppm.
Claims (9)
1. New intermediates of the formula I
in which formula X is halogen, e.g. chlorine or bromine, or another good leaving group, e.g.
and R1 and R2 are hydrogen or lower alkyl, with the proviso that when X is chlorine, at least one of
R1 and R2 is lower alkyl.
2. Intermediate according to claim 1 which is bis(chlorosulfate)methane.
3. Intermediate according to claim 1 which is a-chloroethylchlorosulfate.
4. Intermediate according to claim 1 which is bromomethyl chlorosulfate.
5. Method for producing a compound of formula I
in which formula X is halogen, e.g. chlorine or bromine, or another good leaving group, e.g.
and R1 and R2 are hydrogen or lower alkyl, wherein chlorosulfonic acid is reacted with a compound of formula III
in which formula R1, R2 and X have the above meanings, and Y stands for a better leaving group than X, the reaction being performed with or without a solvent present depending upon the reactants in question, and at a temperature between -200C and 100 C.
6. Method for producing a compound of formula I of claim 5, in which X stands for halogen, in particular chlorine, wherein an alkyl chlorosulfate of the formula V
in which R1 and R2 are as above, is halogenated photochemically, if desired with the alkyl chlorosulfate dissolved in a suitable, to the reaction inert organic solvent, such as carbon tetrachloride, into which the desired halogen is introduced with simultaneous irradiation of the solution, whereafter, when the reaction has taken place, the product is isolated e.g. by distillation.
7. Method for producing a compound of formula I of claim 5, in which.R1=R2=H and
wherein chloromethyl chlorosulfate is reacted with sulphur trioxide, isolating the reaction product from the reaction mixture by distillation at low pressure.
8. A new intermediate of the formula I defined in claim 1 substantially as hereinbefore described in any one of the foregoing examples.
9. Method for producing a compound of formula I defined in claim 1 substantially as hereinbefore described in any one of the foregoing examples.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08308615A GB2137193B (en) | 1983-03-29 | 1983-03-29 | Chlorosulphonic acid esters |
| SE8401280A SE8401280L (en) | 1983-03-29 | 1984-03-07 | INTERMEDIATES AND THE PROCEDURE FOR PRODUCING THEREOF |
| IT8467298A IT8467298A0 (en) | 1983-03-29 | 1984-03-27 | INTERMEDIATE COMPOUNDS PARTICULARLY FOR THE PREPARATION OF ALPHA-HALOALKYLESTERS OR ALKYLENIC DIESTERS OF CARBOXYLIC ACIDS AND PROCEDURE FOR THEIR PREPARATION |
| DE19843411242 DE3411242A1 (en) | 1983-03-29 | 1984-03-27 | ALKYL CHLORINE SULFATE INTERMEDIATE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF |
| JP59062079A JPS59184156A (en) | 1983-03-29 | 1984-03-28 | Chlorosulfonic acid ester and manufacture |
| FR8404872A FR2543547A1 (en) | 1983-03-29 | 1984-03-28 | NOVEL MONO AND BIS-CHLOROSULFONATES, USEFUL AS INTERMEDIATES, AND PROCESSES FOR THEIR PREPARATION |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08308615A GB2137193B (en) | 1983-03-29 | 1983-03-29 | Chlorosulphonic acid esters |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8308615D0 GB8308615D0 (en) | 1983-05-05 |
| GB2137193A true GB2137193A (en) | 1984-10-03 |
| GB2137193B GB2137193B (en) | 1986-05-08 |
Family
ID=10540408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08308615A Expired GB2137193B (en) | 1983-03-29 | 1983-03-29 | Chlorosulphonic acid esters |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS59184156A (en) |
| DE (1) | DE3411242A1 (en) |
| FR (1) | FR2543547A1 (en) |
| GB (1) | GB2137193B (en) |
| IT (1) | IT8467298A0 (en) |
| SE (1) | SE8401280L (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704456A (en) * | 1985-11-22 | 1987-11-03 | Pfizer Inc. | Process for sultamicillin intermediate |
| US4942229A (en) * | 1987-11-25 | 1990-07-17 | Yoshitomi Pharmaceutical Industries, Ltd. | Process for the production of penicillanic acid compounds |
| CN107986995A (en) * | 2017-12-08 | 2018-05-04 | 和夏化学(太仓)有限公司 | A kind of preparation method of methyl dichloro sulphonic acid ester |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548258A (en) * | 2019-02-12 | 2020-08-18 | 北京旭阳科技有限公司 | Use of sulfonyl type compounds as chlorination reagents |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1355204A (en) * | 1970-08-31 | 1974-06-05 | Stauffer Chemical Co | Antidote compositions and method of use with herbicides |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238240A (en) * | 1963-09-20 | 1966-03-01 | Pennsalt Chemicals Corp | Perhaloalkyl chlorosulfates and fluorosulfates |
-
1983
- 1983-03-29 GB GB08308615A patent/GB2137193B/en not_active Expired
-
1984
- 1984-03-07 SE SE8401280A patent/SE8401280L/en not_active Application Discontinuation
- 1984-03-27 DE DE19843411242 patent/DE3411242A1/en not_active Withdrawn
- 1984-03-27 IT IT8467298A patent/IT8467298A0/en unknown
- 1984-03-28 JP JP59062079A patent/JPS59184156A/en active Pending
- 1984-03-28 FR FR8404872A patent/FR2543547A1/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1355204A (en) * | 1970-08-31 | 1974-06-05 | Stauffer Chemical Co | Antidote compositions and method of use with herbicides |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704456A (en) * | 1985-11-22 | 1987-11-03 | Pfizer Inc. | Process for sultamicillin intermediate |
| US4942229A (en) * | 1987-11-25 | 1990-07-17 | Yoshitomi Pharmaceutical Industries, Ltd. | Process for the production of penicillanic acid compounds |
| EP0382863A1 (en) * | 1987-11-25 | 1990-08-22 | Yoshitomi Pharmaceutical Industries, Ltd. | Process for the production of penicillanic acid compounds |
| CN107986995A (en) * | 2017-12-08 | 2018-05-04 | 和夏化学(太仓)有限公司 | A kind of preparation method of methyl dichloro sulphonic acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3411242A1 (en) | 1985-01-10 |
| GB2137193B (en) | 1986-05-08 |
| JPS59184156A (en) | 1984-10-19 |
| IT8467298A0 (en) | 1984-03-27 |
| SE8401280D0 (en) | 1984-03-07 |
| SE8401280L (en) | 1984-09-30 |
| GB8308615D0 (en) | 1983-05-05 |
| FR2543547A1 (en) | 1984-10-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |