DD152336A5 - Verfahren zur herstellung von diesterdiamiden - Google Patents

Verfahren zur herstellung von diesterdiamiden Download PDF

Info

Publication number: DD152336A5
Authority: DD; German Democratic Republic
Prior art keywords: diester; ester salt; solvent; catalysts; diamide
Prior art date: 1979-09-10

Application number

DD80223155A

Other languages

German (de)

English (en)

Inventor

Franco Cognigni

Armando Mariano

Original Assignee

Anic Spa

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1979-09-10

Filing date

1980-08-06

Publication date

1981-11-25

1980-08-06 Application filed by Anic Spa filed Critical Anic Spa

1981-11-25 Publication of DD152336A5 publication Critical patent/DD152336A5/de

Links

238000004519 manufacturing process Methods 0.000 title abstract description 4
150000001470 diamides Chemical class 0.000 title 1
239000002904 solvent Substances 0.000 claims abstract description 32
-1 diester diamides Chemical class 0.000 claims abstract description 31
239000003054 catalyst Substances 0.000 claims abstract description 17
238000005406 washing Methods 0.000 claims abstract description 13
230000015572 biosynthetic process Effects 0.000 claims abstract description 12
150000005690 diesters Chemical class 0.000 claims abstract description 11
238000003786 synthesis reaction Methods 0.000 claims abstract description 10
239000012452 mother liquor Substances 0.000 claims abstract description 7
150000004985 diamines Chemical class 0.000 claims abstract description 5
239000012535 impurity Substances 0.000 claims abstract description 3
238000001914 filtration Methods 0.000 claims description 11
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
238000000034 method Methods 0.000 claims description 7
238000002360 preparation method Methods 0.000 claims description 6
239000002244 precipitate Substances 0.000 claims description 4
238000011084 recovery Methods 0.000 claims description 2
125000003158 alcohol group Chemical group 0.000 claims 1
239000003153 chemical reaction reagent Substances 0.000 abstract description 10
239000000047 product Substances 0.000 abstract description 7
OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 2
239000007795 chemical reaction product Substances 0.000 abstract 1
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
239000000203 mixture Substances 0.000 description 22
WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 15
239000000243 solution Substances 0.000 description 9
238000006243 chemical reaction Methods 0.000 description 8
229910052751 metal Inorganic materials 0.000 description 6
239000002184 metal Substances 0.000 description 6
229920000642 polymer Polymers 0.000 description 5
150000001298 alcohols Chemical class 0.000 description 4
RCRBCNZJGBTYDI-UHFFFAOYSA-L dilithium;terephthalate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 RCRBCNZJGBTYDI-UHFFFAOYSA-L 0.000 description 4
NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
229930195733 hydrocarbon Natural products 0.000 description 4
150000002430 hydrocarbons Chemical class 0.000 description 4
229910052744 lithium Inorganic materials 0.000 description 4
UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
239000006227 byproduct Substances 0.000 description 3
239000000178 monomer Substances 0.000 description 3
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
239000003513 alkali Substances 0.000 description 2
229910052784 alkaline earth metal Inorganic materials 0.000 description 2
150000004703 alkoxides Chemical class 0.000 description 2
125000000217 alkyl group Chemical group 0.000 description 2
125000004432 carbon atom Chemical group C* 0.000 description 2
238000004821 distillation Methods 0.000 description 2
150000002148 esters Chemical class 0.000 description 2
239000000835 fiber Substances 0.000 description 2
230000007062 hydrolysis Effects 0.000 description 2
238000006460 hydrolysis reaction Methods 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
239000007788 liquid Substances 0.000 description 2
239000000463 material Substances 0.000 description 2
150000003839 salts Chemical class 0.000 description 2
239000002594 sorbent Substances 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical class C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 1
WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 1
FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
LQLQDKBJAIILIQ-UHFFFAOYSA-N Dibutyl terephthalate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C=C1 LQLQDKBJAIILIQ-UHFFFAOYSA-N 0.000 description 1
DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
125000001931 aliphatic group Chemical group 0.000 description 1
150000001342 alkaline earth metals Chemical class 0.000 description 1
125000003118 aryl group Chemical group 0.000 description 1
230000000903 blocking effect Effects 0.000 description 1
229910052799 carbon Inorganic materials 0.000 description 1
230000003197 catalytic effect Effects 0.000 description 1
238000005119 centrifugation Methods 0.000 description 1
238000010908 decantation Methods 0.000 description 1
230000006866 deterioration Effects 0.000 description 1
ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
230000003670 easy-to-clean Effects 0.000 description 1
150000002334 glycols Chemical class 0.000 description 1
ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
BBCLUPOZFBVMPB-UHFFFAOYSA-M lithium 4-methoxycarbonylbenzoate Chemical compound C(C1=CC=C(C(=O)[O-])C=C1)(=O)OC.[Li+] BBCLUPOZFBVMPB-UHFFFAOYSA-M 0.000 description 1
150000002642 lithium compounds Chemical class 0.000 description 1
JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
150000002739 metals Chemical class 0.000 description 1
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
239000010413 mother solution Substances 0.000 description 1
BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
238000000746 purification Methods 0.000 description 1
238000004064 recycling Methods 0.000 description 1
238000000926 separation method Methods 0.000 description 1
229910052708 sodium Inorganic materials 0.000 description 1
239000011734 sodium Substances 0.000 description 1
239000011877 solvent mixture Substances 0.000 description 1
239000000600 sorbitol Substances 0.000 description 1
238000009987 spinning Methods 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Chemical Kinetics & Catalysis (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Polyamides (AREA)
Steroid Compounds (AREA)

DD80223155A 1979-09-10 1980-08-06 Verfahren zur herstellung von diesterdiamiden DD152336A5 (de)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
IT25570/79A IT1123574B (it)	1979-09-10	1979-09-10	Processo per la produzione di diesterediammidi

Publications (1)

Publication Number	Publication Date
DD152336A5 true DD152336A5 (de)	1981-11-25

Family

ID=11217125

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
DD80223155A DD152336A5 (de)	1979-09-10	1980-08-06	Verfahren zur herstellung von diesterdiamiden

Country Status (21)

Country	Link
US (1)	US4614815A (cs)
JP (1)	JPS5640649A (cs)
AU (1)	AU536158B2 (cs)
BE (1)	BE884650A (cs)
CA (1)	CA1172650A (cs)
CH (1)	CH650769A5 (cs)
CS (1)	CS221975B2 (cs)
DD (1)	DD152336A5 (cs)
DE (1)	DE3029970C2 (cs)
DK (1)	DK158660C (cs)
FR (1)	FR2468583A1 (cs)
GB (1)	GB2058053B (cs)
HU (1)	HU191172B (cs)
IT (1)	IT1123574B (cs)
LU (1)	LU82686A1 (cs)
NL (1)	NL8004512A (cs)
NO (1)	NO151197C (cs)
SE (1)	SE439304B (cs)
SU (1)	SU1389676A3 (cs)
YU (1)	YU41446B (cs)
ZA (1)	ZA804455B (cs)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4767839A (en) *	1987-07-06	1988-08-30	Allied-Signal Inc.	Alternating aliphatic-aromatic poly(esteramide)
JPH04500359A (ja) *	1988-11-14	1992-01-23	ザ・トラステイーズ・オブ・コロンビア・ユニヴアーシテイ・イン・ザ・シテイ・オブ・ニユー・ヨーク	最終分化に有効な新規誘発物質およびその使用方法
US5608108A (en) *	1988-11-14	1997-03-04	Sloan-Kettering Institute For Cancer Research	Potent inducers of terminal differentiation and method of use thereof
DE4024466C2 (de) *	1990-07-30	1995-04-20	Dainippon Ink & Chemicals	Thermisch härtbare Mischungen aus polyfunktionellen Formamiden und aromatischen Mono-, Di- oder Polyglycidylethern und deren Verwendung
USRE38506E1 (en)	1991-10-04	2004-04-20	Sloan-Kettering Institute For Cancer Research	Potent inducers of terminal differentiation and methods of use thereof
US5700811A (en) *	1991-10-04	1997-12-23	Sloan-Kettering Institute For Cancer Research	Potent inducers of terminal differentiation and method of use thereof
US5369108A (en) *	1991-10-04	1994-11-29	Sloan-Kettering Institute For Cancer Research	Potent inducers of terminal differentiation and methods of use thereof
CA2189072A1 (en) *	1994-06-17	1995-12-28	Exxon Chemical Patents Inc.	Amidation of ester functionalized hydrocarbon polymers
US5852155A (en) *	1995-03-01	1998-12-22	General Electric Company	Compositions of polyesteramides
US5744068A (en) *	1996-01-24	1998-04-28	General Electric Company	Blends of polyphenylene ethers and polyesteramides
US5731389A (en) *	1996-04-24	1998-03-24	General Electric Company	Blends of polyesters and polyesteramides, optionally with polycarbonates
WO1997041166A1 (en) *	1996-04-30	1997-11-06	Toray Industries, Inc.	Polyester amide copolymer and process for the production thereof, polyester amide monomer and process for the production thereof, and polyester amide resin composition
NZ517613A (en) *	1999-09-08	2004-01-30	Sloan Kettering Inst Cancer	Novel class of cytodifferentiating agents and histone deacetylase inhibitors, and methods of use thereof
WO2004089293A2 (en) *	2003-04-01	2004-10-21	Memorial Sloan-Kettering Cancer Center	Hydroxamic acid compounds and methods of use thereof
JPWO2013153754A1 (ja) *	2012-04-11	2015-12-17	出光興産株式会社	β−アルコキシプロピオンアミド類の製造方法
WO2015022119A1 (en) *	2013-08-16	2015-02-19	Dsm Ip Assets B.V.	Process for producing a thermoplastic polymer containing segments of a diamide
KR101568357B1 (ko) *	2013-11-25	2015-11-12	롯데케미칼 주식회사	신규 화합물 및 이의 제조방법

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2925405A (en) *	1955-04-26	1960-02-16	Eastman Kodak Co	Linear polyesters containing an alkylene diamine group and manufacture thereof
US2848439A (en) *	1955-04-26	1958-08-19	Eastman Kodak Co	Linear polyesters of bis (nu-p-carboxyphenyl) alkylene diamides and manufacture thereof
US2839508A (en) *	1955-04-26	1958-06-17	Eastman Kodak Co	Copolyesters of a glycol, an alkylene diamine dicarboxylate and a sulfone ester
US2861055A (en) *	1955-04-26	1958-11-18	Eastman Kodak Co	Copolyesters of a glycol and an alkylene diamine dicarboxylate containing isophthalate modifier and their preparation
US2851443A (en) *	1955-04-26	1958-09-09	Eastman Kodak Co	Quenchable copolyesters of a glycol, terephthalic acid and an alkylene diamine dicarboxylate and their preparation
US2856385A (en) *	1956-05-10	1958-10-14	Eastman Kodak Co	Polyester-amides of n,n'-bis-(p-carboxybenzoyl) alkylenediamines, glycols and diamines
BE773738A (fr) *	1970-10-13	1972-01-31	Snam Progetti	Procede de fabrication de monomeres utilisables dans la synthese des polyesters-amides reguliers et polyesters amides obtenuspar ce procede

1979
- 1979-09-10 IT IT25570/79A patent/IT1123574B/it active
1980
- 1980-07-17 CH CH5485/80A patent/CH650769A5/it not_active IP Right Cessation
- 1980-07-21 DK DK313380A patent/DK158660C/da not_active IP Right Cessation
- 1980-07-22 NO NO802196A patent/NO151197C/no unknown
- 1980-07-22 AU AU60686/80A patent/AU536158B2/en not_active Ceased
- 1980-07-23 SE SE8005346A patent/SE439304B/sv not_active IP Right Cessation
- 1980-07-23 ZA ZA00804455A patent/ZA804455B/xx unknown
- 1980-07-24 CA CA000356970A patent/CA1172650A/en not_active Expired
- 1980-07-24 GB GB8024330A patent/GB2058053B/en not_active Expired
- 1980-07-30 YU YU1925/80A patent/YU41446B/xx unknown
- 1980-08-04 LU LU82686A patent/LU82686A1/fr unknown
- 1980-08-05 FR FR8017294A patent/FR2468583A1/fr active Granted
- 1980-08-06 BE BE0/201664A patent/BE884650A/fr not_active IP Right Cessation
- 1980-08-06 SU SU802957756A patent/SU1389676A3/ru active
- 1980-08-06 HU HU801956A patent/HU191172B/hu not_active IP Right Cessation
- 1980-08-06 CS CS805438A patent/CS221975B2/cs unknown
- 1980-08-06 DD DD80223155A patent/DD152336A5/de unknown
- 1980-08-06 JP JP10724780A patent/JPS5640649A/ja active Granted
- 1980-08-07 NL NL8004512A patent/NL8004512A/nl not_active Application Discontinuation
- 1980-08-07 DE DE3029970A patent/DE3029970C2/de not_active Expired
1982
- 1982-06-07 US US06/385,529 patent/US4614815A/en not_active Expired - Fee Related

Also Published As

Publication number	Publication date
US4614815A (en)	1986-09-30
SE8005346L (sv)	1981-03-11
IT1123574B (it)	1986-04-30
NO802196L (no)	1981-03-11
IT7925570A0 (it)	1979-09-10
JPS5640649A (en)	1981-04-16
FR2468583A1 (fr)	1981-05-08
NO151197C (no)	1985-02-27
HU191172B (en)	1987-01-28
GB2058053A (en)	1981-04-08
DK313380A (da)	1981-03-11
FR2468583B1 (cs)	1984-02-17
YU192580A (en)	1984-02-29
NL8004512A (nl)	1981-03-12
DK158660B (da)	1990-07-02
CS221975B2 (en)	1983-04-29
JPH021136B2 (cs)	1990-01-10
ZA804455B (en)	1981-07-29
DK158660C (da)	1991-01-21
CH650769A5 (it)	1985-08-15
BE884650A (fr)	1981-02-06
CA1172650A (en)	1984-08-14
AU536158B2 (en)	1984-04-19
GB2058053B (en)	1983-10-05
DE3029970C2 (de)	1984-10-04
NO151197B (no)	1984-11-19
LU82686A1 (fr)	1981-03-24
SE439304B (sv)	1985-06-10
SU1389676A3 (ru)	1988-04-15
AU6068680A (en)	1981-03-19
DE3029970A1 (de)	1981-03-12
YU41446B (en)	1987-06-30

Publication	Publication Date	Title
DD152336A5 (de)	1981-11-25	Verfahren zur herstellung von diesterdiamiden
DE69311585T2 (de)	1998-02-12	Verfahren zur Reinigung von Acrylsäure zu hoher Reinheit bei der Herstellung von Acrylsäure
DE3885151T2 (de)	1994-02-24	Methode zur Herstellung von Methacrylatestern.
EP0562504A2 (de)	1993-09-29	Verfahren zur kontinuierlichen Herstellung von C1-bis C4-Alkylestern höherer Fettsäuren
DE69010046T2 (de)	1994-10-13	Reinigungs- und Herstellungsverfahren von Methylmethacrylat.
DE3050670C2 (cs)	1988-01-07
DE60022147T2 (de)	2006-06-01	Organophosphor- Zusammensetzung, Verfahren zur Herstellung einer Organophosphor-Verbindung, Polyester-Zusammensetzung und Verfahren zur Herstellung davon
DE2547540A1 (de)	1976-05-13	Verfahren zur herstellung von hydroxypivaldehyd
DE4019781A1 (de)	1992-01-02	Verfahren zur herstellung von monoethylenisch ungesaettigten carbonsaeureestern
DE1258854B (de)	1968-01-18	Verfahren zur kontinuierlichen Herstellung von Alkoholen durch Hydrolyse von Aluminiumalkoxiden in einem homogenen System aus n-Butanol und Wasser
EP0779102B1 (de)	2000-07-05	Verfahren zur Wiedergewinnung von bei der Herstellung von N-Acyl-alpha-aminosäurederivaten durch Amidocarbonylierung eingesetzten Cobaltcarbonylkatalysatoren
DE2104020C3 (de)	1975-09-18	Verfahren zur Herstellung von Salzen von Sulfoalkylacrylat oder -methacrylat
DE3051036C2 (cs)	1988-03-31
DE69013187T2 (de)	1995-03-16	Verfahren zur Herstellung von Alkylenglykolmonosorbaten.
DE2539027A1 (de)	1976-03-11	Verfahren zum reinigen von diaminomaleinsaeuredinitril
DE3878088T2 (de)	1993-07-22	Reinigung von diphenylphthalaten.
DE69010165T2 (de)	1994-10-06	Verfahren zur Reinigung von 3,4,5,6-Tetrahydrophthalsäureanhydrid.
DE2604751C2 (cs)	1987-11-05
DE867994C (de)	1953-02-23	Verfahren zur Herstellung organischer Thiophosphorsaeureester
DE973361C (de)	1960-02-04	Verfahren zur Herstellung von Terephthalsaeuredimethylester
DE956504C (de)	1957-01-17	Verfahren zur Herstellung wertvoller Ester mit tiefem Stockpunkt
AT340905B (de)	1978-01-10	Verfahren zur reinigung von rohen, hochsiedenden carbonsaureestern
DE600867C (de)	1934-08-03	Verfahren zum Faellen von organischen Celluloseestern aus der Reaktionsmischung
DE871007C (de)	1953-03-19	Verfahren zur Abtrennung schwer entfernbarer Verunreinigungen aus roher Dehydracetsaeure
DE619348C (de)	1935-09-28	Verfahren zur Herstellung von reinem Diacetyl aus Holzessig oder anderen Diacetyl enthaltenden Gemischen