text:
You can initiate your own astonishing locale supported business organization and wallow in the commercial enterprise state that it can hand over you. The options going spare for you in starting a house based online enterprise are numerous. You conscionable have to spend a lot of incident and force in place your domicile enterprise and you can later lounge and takings pleasure from the binary profits streams coming your way.
There is a destiny to bring in in Internet marketing. The utmost important original rung in establishing your habitation supported Internet commercialism commercial is to investigation and do a lot of browse. Find out what Internet commercialism schemes and programs are free for you. Make certain you decide on the furthermost apropos system that suit your needs, interests, and monetary fund. Select a mercantilism concern that is uncomplicated to means and contribute blue-chip benefaction for its affiliates same gratuitous websites, a 24/7 bargain hunter vigilance assistance, updated product information, and merchandising tools approaching downloadable eBooks, surprising banners and buttons, and email templates. There are heaps programs that speech act these kinds of employment and if you insight one, submerge in and move into your firm.
Another proceeds river selection you can do is to set up an online stash. This could be your own online purchasing souk. You can later move in profitable eBay auctions and merchandising. But be certain to find out what open market niche you are active to start. Once you want on what hue of products you will deal in on Ebay, guarantee that you have a safe contributor that can dispense you agreement cellar prices. You essential too plug your products in diverse online classified ads and submit your website to through investigate engines.Post ads:
Janska Hooded Scarf, Black, OS / Cotton 6 Pairs Camouflage Camo Army Crew Ladies Mid Calf / YMI Juniors Core Boot Jean / HS Women Fashion Ankle Socks Wild Animal Print Design / bebe Sheer Rib Tights / DG Eyewear Tortoise Brown Frame Sunglasses 37163 and 1 / My Michelle Juniors Sleeveless Dress / Large Rectangular Thin Plastic Frame Clear Lens Fashion / Tommy Hilfiger Women V-neck Striped T-shirt / Jockey staycool Bikini - 3 pack / KUT from the Kloth Women's Fame Jacket / Allegra K Woman Irregular Hem Zebra Print Cover up Shirt / Elegant Eggplant Reversible Paisley Pashmina Silk Shawl / Arbor Outline Tank Top - Women's / Gore Bike Wear Women's Contest So Lady Jacket / J Brand 811 Mid-Rise Skinny in Blue Bell / Barely There Women's Customflex Fit Active Wirefree
These hole based company opportunities can underwrite a dense and stabilized profits for you. Persist and be resourceful so that your own household supported company will replace and boom.Post ads:
Quiksilver OG Mountain Pullover Sweatshirt - Women's / Dreams and Company Plus Size Knit and Fleece Pajamas / Key Chain with Leather Id / Card Case By Mundi / Hue Opaque Sheer to Waist Opaque Tight / Jones New York Women's Suede To Nutria / Carole Hochman Women's Long Hooded Wrap Robe Robe / Torrid Plus Size Black And Brown Reversible Belt / Mammut Women's Ultimate Hoody / Columbia Women's Ombre Hombre Turtleneck Sweater / Browning Hosiery Women's Ladies Heavy Weight Wool Blend / Fleur't Women's Top Drawer Boy Pant / Carhartt Women's Tomboy Jacket / Luxury Lane Women's Cashmere Lined Leather Gloves with Bow / Hailey Jeans Co Womens 2-pc Velour Track Suit / Shaping Capri Leggings / Tuga Women's UPF 50+ UV Sun Protective Long Sleeve / Elle Macpherson Intimates Momamia Maternity Bra


text:
If an item you ordered from TextbookRush does not meet your expectations due to an error on our part, simply fill out a return request and then return it by mail within 30 days of ordering it for a full refund of item cost.
Learn more about our returns policy
Description: Barcelonais Robert Hughes's monumentally informed and irresistibly opinionated guide to the most un-Spanish city in Spain. Hughes scrolls through Barcelona's often violent history; tells the stories of its kings, poets, magnates, and revolutionaries; and ushers readers through municipal landmarks that range from Antoni Gaudi's sublimely surreal cathedral to a postmodern restaurant with a glass-walled urinal. The result is a work filled with the attributes of Barcelona itself: proportion, humor, and seny-- the Catalan word for triumphant common sense.
Limited time offer:
Get the first one free! (?)
All the information you need in one place! Each Study Brief is a summary of one specific subject; facts, figures, and explanations to help you learn faster.
List price: $21.00Publisher: Knopf Doubleday Publishing GroupPublication date: 3/9/1993Binding: PaperbackPages: 592Size: 5.25" wide x 8.00" long x 1.25" tall Weight: 1.430Language: English
Robert Hughes was born on July 28, 1938 in Sydney, Australia. He attended St. Ignatius College and Sydney University before embarking on a career as a freelance writer. In 1970, he became the art critic for Time magazine. Hughes garnered wide acclaim for his book and television series The Shock of the New. Chronicling Hughes's vast knowledge and experience with modern art, The Shock of the New presents the author's views and opinions of many facets of art including contemporary architecture. Hughes's other ground-breaking books include American Visions: The Epic History of Art in America and Culture of Complaint: The Fraying of America. In these, Hughes presents his own unique brand of criticism, not merely on art, but also on American politics. Everyone from Jesse Helms to Ronald Reagan undergoes analysis, and the state of politics in the late 20th century is often lamented.
*A minimum purchase of $35 is required. Shipping is provided via FedEx SmartPost®
and FedEx Express Saver®. Average delivery time is 1 – 5 business days, but
is not guaranteed in that timeframe. Also allow 1 - 2 days for processing. Free shipping is eligible only in the continental United States and excludes
Hawaii, Alaska and Puerto Rico. FedEx service marks used by permission."Marketplace"
orders are not eligible for free or discounted shipping.
Learn more about the TextbookRush

subset: commoncrawl


text:
Need help?
Contact us or call 0333 400 9500
Contact us or call 0333 400 9500
|FM reception
|87.5-108 Mhz
|AM reception
|531 KHz -1611 KHz
|SW reception
|5.80-7.50 MHz
|9.30-10.05 MHz
|11.55-12.20 MHz
|13.40-14.00 MHz
|15.00-15.80 MHz
|17.40-18.05 MHz
|21.20-21.80 MHz
|Power Sources
|Wind-up power
|Solar panel
|Internal re-chargeable battery pack
|3 x AAA batteries (not included)
|Dimensions (mm)
|158 x 165 x 69
|Weight (g)
|Item code
|Item name
|Eton Solarlink FR360 Shortwave, FM and AM Radio (Used)
At Maplin, we're always looking for innovations and technology that can help your business work more efficiently.
With a dedicated business team and special services available only to business customers, you can access our electronics and technology solutions through our wide network of over 200 stores, our website with more than 20,000 products or though your personal account manager over the phone.
Working with organisations for nearly 30 years, Maplin offers a nationwide range of benefits to our business users:
Contact our business team on
0333 400 9740 to open an account or discuss your business needs.
To receive your free copy of the Maplin Catalogue just call 0333 400 9740.


text:
The LS21 Valk is a VSA submachine gun introduced in Killzone: Shadow Fall, and the successor to the M66-SD Submachine Gun to which it bears a resemblance.
Weapon InformationEdit
The LS21 Valk is one of three submachine guns in Shadow Fall, and the first of two that are available to the Assault class in multiplayer. The Valk has a high rate of fire, but lacks stopping power and has a smaller magazine capacity. It is quite compact and a solid choice for players that prefer to rush around the map with an aggressive playstyle. The Valk has a unique, built-in burst fire feature. You can tap the fire button to fire a burst of three bullets, or hold the trigger down for fully automatic firing. The LS21 has 3 scopes and 2 underbarrels. The gun is sometimes equiped with a laser dot scope, a holo scope and a AGOG scope and for under barrels are a shotgun underbarrel and a laser underbarrel which increases its accurcy.


text:
Describe the brave deed which is carried out by David in chapter 4.
Why did the man try and drown the puppy?
What is a 'queen cat' and why would people not want to keep them?
Which three incidents prove that David has a caring and responsible side?
Which incidents prove that David can also be defiant, disobedient and dishonest?
What does a boy do to David after a stone accidentally hits him and what happens to David afterwards and who intervenes?
What does David refuse to do (regarding Dadda)


text:
Satish Verma
Satish Verma (5-6-1935)
» Click to list general statistics » OR, select a date :
Raas! *
The evening opens a wound,
a secret agony.
It neither heals nor gives solace.
The sacred whore who liberates herself
read more >>
- Hits: Number of visitors who read the poem on the given date.
- Posts: Number of visitors who posted the poem to a friend (via e-mail) on the given date.
- Dates that have "0" hits may not be shown on the list.
- Dates, poems and poets that have "0" hits may not be shown on the list. Statistics are generated daily.


text:
Sarah, blogger for Sweet Blonde's Fit Life, has become quite an avid runner since she began her quest to become healthier a few years back. While she loves running in the summer, she knows that there are some major essentials that she can't live without to get through her runs in the heat. To no surprise, OOFOS made it on her list of summer running essentials.
Sarah makes sure to pack a pair of OOFOS OOriginal Sport sandals to pull out after her runs and save her feet from swelling and soreness. She says,
"I am loving the OOFOS Sport Sandal. It is super cushiony and feels like a dream! It's also biomechanically engineered to alleviate foot stress and soreness."
To read Sarah's full review of OOFOS, click the photo below!


text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 31, 1991
|Filing date
|Mar 28, 1990
|Priority date
|Mar 26, 1987
|Fee status
|Also published as
|Publication number
|Vincent Desobry, Kurt Dietliker, Rinaldo Husler, Werner Rutsch, Manfred Rembold, Franciszek Sitek
|Original Assignee
|Ciba-Geigy Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (5), Referenced by (67), Classifications (78), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation of application Ser. No. 403,004, filed Sept 5, 1989, which is a continuation of Ser No. 172,618, filed Mar. 24, 1988, both now abandoned.
The invention relates to novel derivatives of α-aminoacetophenone which have an allyl or aralkyl group in the α-position, and to their use as photoinitiators for the photopolymerization of ethylenically unsaturated compounds, in particular for photocuring pigmented systems, such as printing inks or white lacquer.
Derivatives of α-aminoacetophenone are known from EP-A-3,002 as photoinitiators for ethylenically unsaturated compounds. If these compounds have in their 4-position of the phenyl radical substituents containing sulfur or oxygen, the compounds are particularly suitable as photoinitiators for pigmented photocurable systems (EP-A-88,050 and 117,233), for example for UV-curable printing inks.
Derivatives of α-aminoacetophenone which have an amino group in the 4-position of the phenyl radical are described in EP-A-138,754. These compounds are used in combination with photosensitizers from the aromatic carbonyl compound class.
It has now been found that of this general class of α-aminoacetophenones, those which contain at least one alkenyl or aralkyl group in the α-position have a particularly high activity as photoinitiators. These compounds are especially suitable for use in printing inks.
The compounds are specifically those of the formula I, II, III or IIIa, ##STR2## in which Ar1 is an aromatic radical of the formula IV, V, VI or VII, ##STR3## in which X is a divalent radical of the formula ##STR4## Y is C1 -C6 alkylene, cyclohexylene or a direct bond, Y' is xylylene, C4 -C8 alkenediyl, C6 -C10 alkadienediyl, dipentenediyl or dihydroxylylene, U is --O--, --S-- or --N(R17)--, V is --O--, --S--, --N(R17)--, --CO--, --CH2 --, --CH2 CH2 --, C2 -C6 alkylidene or a direct bond, W is unbranched or branched C1 -C7 alkylene or C2 -C6 alkylidene, R1 is either (a) a radical of the formula ##STR5## in which p is zero or 1, or (b) a radical of the formula ##STR6## in which q is 0, 1, 2 or 3, or (c) a radical of the formula ##STR7## in which Ar2 is a phenyl, naphthyl, furyl, thienyl or pyridyl radical which is unsubstituted or substituted by halogen, OH, C1 -C12 alkyl, C1 -C4 alkyl which is substituted by OH, halogen, --N(R11)2, --C1 -C12 alkoxy, --COO(C1 -C18 alkyl), --CO(OCH2 CH2)n OCH3 or --OCO(C1 -C4)alkyl, C1 -C12 alkoxy, C1 -C4 alkoxy which is substituted by --COO(C1 -C18 -alkyl) or --CO(OCH2 CH2)n OCH3, --(OCH2 CH2)n OH, --(OCH2 CH2)n OCH3, C1 -C8 alkylthio, phenoxy, --COO(C1 -C18 alkyl), --CO(OCH2 CH2)n OCH3, phenyl or benzoyl, in which n is 1-20, or (d) together with R2 forms a radical of the formula ##STR8## in which m is 1 or 2, R2 has one of the meanings given for R1 or is C5 -C6 cycloalkyl, C1 -C12 alkyl which is unsubstituted or substituted by C1 -C4 alkoxy, phenoxy, halogen or phenyl, or phenyl which is unsubstituted or substituted by halogen, C1 -C12 alkyl or C1 -C4 alkoxy, R3 is hydrogen, C1 -C12 alkyl, C2 -C4 alkyl which is substituted by hydroxyl, C1 -C4 alkoxy, --CN or --COO(C1 -C4 alkyl), C3 -C5 alkenyl, C5 -C12 cycloalkyl or C7 -C9 phenylalkyl, R4 is C1 -C12 alkyl, C2 -C4 alkyl which is substituted by hydroxyl, C1 -C4 alkoxy, --CN or --COO(C1 -C4 alkyl), C3 -C5 -alkenyl, C5 -C12 cycloalkyl, C7 -C9 phenylalkyl, phenyl or phenyl which is substituted by halogen, C.sub. 1 -C12 alkyl, C1 -C4 alkoxy or --COO(C1 -C4 -alkyl or R4 together with R2 is C1 -C7 alkylene, C7 -C10 phenylalkylene, o-xylylene, 2-butenylene or C2 -C3 oxa- or -azaalkylene, or R3 and R4 together are C3 --C7 alkylene, which can be interrupted by --O--, --S--, --CO-- or --N(R17)- or can be substituted by hydroxyl, C1 -C4 alkoxy or --COO(C1 -C4 alkyl), R5, R6, R7, R8 and R9 independently of one another are hydrogen, halogen, C1 -C12 alkyl, C5 -C6 cycloalkyl, phenyl, benzyl, benzoyl or a group --OR18, --SR19, --SO--R19, --SO2 -R19, --N(R20)(R21), --NH--SO2 --R22 or ##STR9## in which Z is --O--, --S--, --N(R11)--, --N(R11)--R12 --N(R11)-- or ##STR10## in which, in the case where R1 is allyl and R2 is methyl, R5 is not --OCH3, and in the case where R1 is benzyl and R2 is methyl or benzyl, R5 is not --OCH3, --SCH3 or --SO--CH3, R10 is hydrogen, C1 -C12 alkyl, halogen or C2 -C8 alkanoyl, R11 is hydrogen, C1 -C8 alkyl, C3 -C5 alkenyl, C7 -C9 phenylalkyl, C1 -C4 hydroxyalkyl or phenyl, R12 is unbranched or branched C2 -C16 alkylene, which can be interrupted by one or more --O--, --S-- or --N(R11)--, R13 is hydrogen, C1 -C8 alkyl or phenyl, R14, R15 and R16 independently of one another are hydrogen or C1 -C4 -alkyl, or R14 and R15 together are C3 -C7 alkylene, R17 is hydrogen, C1 -C12 alkyl, which can be interrupted by one or more --O--, C3 -C5 -alkenyl, C7 -C9 phenylalkyl, C1 -C4 hydroxyalkyl, --CH2 CH2 CN, --CH2 CH2 COO(C1 -C4 alkyl), C2 -C8 alkanoyl or benzoyl, R18 is hydrogen, C1 -C12 alkyl, C1 -C6 alkyl which is substituted by --CN, --OH, C1 -C4 alkoxy, C3 -C6 alkenoxy, --OCH2 CH2 CN, --OCH2 CH2 COO(C1 -C4 alkyl), --COOH or --COO(C1 -C4 alkyl), --(CH2 CH2 O)n H where n=2-20, C2 -C8 alkanoyl, C3 -C12 alkenyl, cyclohexyl, hydroxycyclohexyl, phenyl, phenyl which is substituted by halogen, C1 -C12 alkyl or C1 -C4 alkoxy, C7 -C9 phenylalkyl or --Si(C1 -C8 alkyl)r (phenyl)3-r where r=1, 2 or 3, R19 is hydrogen, C1 -C12 alkyl, C3 -C12 alkenyl, cyclohexyl, C1 -C6 alkyl which is substituted by --SH, --OH, --CN, --COO(C1 -C4 alkyl), C1 -C4 alkoxy, --OCH2 CH2 CN or --OCH2 CH2 COO(C1 -C4 alkyl), phenyl, phenyl which is substituted by halogen, C1 -C12 alkyl or C1 -C4 alkoxy or C7 -C9 phenylalkyl, R20 and R21 independently of one another are hydrogen, C1 -C12 alkyl, C2 -C4 hydroxyalkyl, C2 -C10 alkoxyalkyl, C3 -C5 alkenyl, C5 -C12 cycloalkyl, C7 -C9 phenylalkyl, phenyl, phenyl which is substituted by halogen, C1 -C12 alkyl or C1 -C4 alkoxy, C2 -C3 alkanoyl or benzoyl, or R20 and R21 together are C2 -C8 alkylene, which can be interrupted by --O--, --S-- or --N(R17)--, or can be substituted by hydroxyl, C1 -C4 alkoxy or --COO(C1 -C4 alkyl) and R22 is C1 -C18 alkyl, phenyl which is unsubstituted or substituted by halogen, C1 -C12 alkyl or C1 -C8 alkoxy or naphthyl, or an acid addition salt of such a compound, in particular compounds of the formula I in which Ar1 is a group of the formula IV, V or VII and R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, V, U and W are as defined above.
C1 -C4 Alkyl R14, R15 and R16 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
C1 -C8 Alkyl R2, R11 and R13 can moreover also be, for example, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl or 2,2,4,4-tetramethylbutyl. C1 -C12 Alkyl R3, R4, R5, R6, R7, R8, R9, R10, R17, R18, R19, R20 and R21 can moreover also be, for example, nonyl, decyl, isodecyl, undecyl or dodecyl.
C3 -C5 Alkenyl R3, R4, R1, R17, R20 and R21 can be, for example, allyl, methallyl, crotyl or dimethylallyl, allyl being preferred. C3 -C12 Alkenyl R18 and R19 can moreover also be, for example, hexenyl, octenyl or decenyl.
C5 -C6 Cycloalkyl R2, R5, R6, R7, R8 and R9 are, in particular, cyclohexyl. C5 -C12 Cycloalkyl R3, R4, R20 and R21 can moreover also be, for example, cyclooctyl or cyclododecyl.
C7 -C9 Phenylalkyl R3, R4, R17, R18, R19, R20 and R21 is, in particular, benzyl.
C1 -C6 Alkylene Y can be, for example, methylene, or di-, tri-, tetra-, penta- or hexamethylene. C1 -C7 Alkylene W can be, for example, methylene, ethylene, 1,2-propylene or 1,2-hexylene.
C2 -C6 Alkylidene V and W can be, for example, ethylidene, propylidene, butylidene, isobutylidene or hexylidene.
Examples of Ar2 are the groups phenyl, 1-naphthyl, 2-naphthyl, 2-furyl, 2-thienyl, 3-pyridyl, 4-chlorophenyl, tolyl, 4-isopropylphenyl, 4-octylphenyl, 3-methoxyphenyl, 4-phenoxyphenyl, 4-phenylphenyl, 4-benzoylphenyl, 4-chloro-1-naphthyl and 4-methyl-2-pyridyl.
Examples of substituted alkyl R2 are the groups 2-methoxyethyl, 3-butoxypropyl, 2-isopropoxyethyl, 4-phenoxybutyl, 2-chloroethyl, 3-chloropropyl, 2-phenylethyl or 3-phenylpropyl. Examples of substituted phenyl R2 are the groups 4-chlorophenyl, 3-methoxyphenyl, 4-tolyl or 4-butylphenyl.
Substituted alkyl R3 and R4 can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxyisobutyl, 2-ethoxyethyl, 2-methoxypropyl, 2- <-butoxyethyl, 2-cyanoethyl, 2-ethoxycarbonylethyl or 2-methoxycarbonylethyl.
Substituted phenyl R4 can be, for example, 3-chlorophenyl, 4-chlorophenyl, 4-tolyl, 4-tert-butylphenyl, 4-dodecylphenyl, 3-methoxyphenyl or 3-methoxycarbonylphenyl.
If R4 together with R2 is alkylene or phenylalkylene, these preferably give, together with the C atom and the N atom to which they are bonded, a 5- or 6-membered heterocyclic ring.
If R3 and R4 together are alkylene or interrupted alkylene, these preferably give, together with the N atom to which they are bonded, a 5-or 6-membered heterocyclic ring, for example a pyrrolidine, piperidine, morpholine, thiomorpholine, piperidone or piperazine ring, which can be substituted by one or more alkyl, hydroxyl, alkoxy or ester groups.
C2 -C8 alkanoyl R10, R17 and R18 can be, for example, propionyl, butyryl, isobutyryl, hexanoyl or octanoyl, but in particular acetyl.
C1 -C4 Hydroxyalkyl or C2 -C4 hydroxyalkyl R11, R17, R20 and R21 can be, for example, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl or 4-hydroxybutyl.
Alkylene or interrupted alkylene R12 can be, for example, ethylene, tri-, tetra-, penta-, hexa-, octa- or dodecamethylene, 2,2-dimethyltrimethylene, 1,3,3-trimethyltetramethylene, 3-oxa-pentamethylene, 3-oxa-heptamethylene, 4,7-dioxa-decamethylene, 4,9-dioxadodecamethylene, 3,6,9,12-tetraoxa-tetradecamethylene, 4-aza-heptamethylene, 4,7-di(methylaza)-decamethylene or 4-thia-heptamethylene.
If R14 and R15 together are C3 -C7 alkylene, they are, in particular, 1,3- or 1,4-alkylene, for example, 1,3-propylene, 1,3-butylene, 2,4-pentylene, 1,3-hexylene, 1,4-butylene, 1,4-pentylene or 2,4-hexylene.
Substituted phenyl R18, R19, R20 and R21 can be, for example, 4-chlorophenyl, 3-chlorophenyl, 4-tolyl, 4-tert-butylphenyl, 4-nonylphenyl, 4-dodecylphenyl, 3-methoxyphenyl or 4-ethoxyphenyl.
An --Si(C1 -C8 alkyl)r (phenyl)3-r group R18 can be, in particular, --Si(CH3)3, --Si(phenyl)2 CH3, --Si(CH3)2 phenyl, --Si(CH3)2 -[C(CH3)2 CH(CH3)2 ] or --Si(phenyl)3.
Substituted C1 -C6 alkyl R18 can be, for example, 2-hydroxyethyl, 2-methoxyethyl or 2-allyloxyethyl.
Substituted C1 -C6 alkyl R19 can be, for example, 2-mercaptoethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, -CH2 CH2 OCH2 CH2 CN or --CH2 CH20 OCH2 CH2 COOCH3.
Alkoxyalkyl R20 and R21 can be, for example, methoxyethyl, ethoxyethyl, 2-ethoxypropyl, 2-butoxyethyl, 3-methoxypropyl or 2-hexyloxyethyl.
C2 -C3 Alkanoyl R20 and R21 are, in particular, acetyl.
Substituted phenyl or naphthyl R22 can be, for example, 4-tolyl, 4-bromophenyl, 3-chlorophenyl, 4-butylphenyl, 4-octylphenyl, 4-decylphenyl, 4-dodecylphenyl, 3-methoxyphenyl, 4-isopropoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, chloronaphthyl, nonylnaphthyl or dodecylnaphthyl.
If R20 and R21 together are alkylene or interrupted alkylene, this forms, together with the N atom to which it is bonded, a heterocyclic ring, preferably a 5- or 6-membered ring, which can be substituted by alkyl, hydroxyl, alkoxy or ester groups. Examples of such rings are a pyrrolidine, piperidine, 4-hydroxypiperidine, 3-ethoxycarbonylpiperidine, morpholine, 2,6-dimethyl-morpholine, piperazine or 4-methylpiperazine ring.
All these compounds have at least one basic amino group and can therefore be converted into the corresponding salts by addition of acids. The acids can be inorganic or organic acids. Examples of such acids are HCl, HBr, H2 SO4, H3 PO4, mono- or polycarboxylic acids, for example, acetic acid, oleic acid, succinic acid, sebacic acid, tartaric acid or CF3 COOH, and sulfonic acids, for example, CH3 SO3 H, C12 H25 SO3 H, p--C12 H25 --C6 H4 --SO3 H, p--CH3 --C6 H4 --SO3 H or CF3 SO3 H.
Preferred compounds of the formula I are those in which Ar1 is a group of the formula IV, R5 and R6 are hydrogen, halogen, C1 -C12 alkyl or a group --OR18, --SR19, --SOR19, --SO2 --R19, --N(R20)(R21), --NHSO2 R22 or ##STR11## in which Z is --O--, --S--, --N(R11 )-- or --N(R11)R12 --N(R11)--, R7 and R8 are hydrogen or halogen, R9 is hydrogen, halogen or C1 -C12 alkyl and R1, R2, R3, R4, R11, R12, R18, R19, R20, R21 and R22 are as defined above, and in the case where R1 is allyl and R2 is methyl, R5 is not --OCH3, and in the case where R1 is benzyl and R2 is methyl or benzyl, R5 is not --OCH3, --SCH3 or --SOCH3.
Of the compounds of the formula I in which Ar1 is a group of the formula IV, in which R5 is a group --OR18, --SR19, --N(R20)(R21) or ##STR12## preferred compounds are those in which R6 is hydrogen, halogen or C1 -C4 -alkyl or has one of the meanings given for R5, R7 and R8 are hydrogen or halogen, R9 is hydrogen or C1 -C4 alkyl, Z is --O--, --S-- or --N(R1 l)--, R1 is either (a) a radical of the formula ##STR13## or (b) a radical of the formula --CH(R13)--Ar2, in which Ar2 is a phenyl radical which is unsubstituted or substituted by halogen, C1 -C4 alkyl methylthio, methoxy or benzoyl, R2 has one of the meanings given for R1 or is C1 -C6 alkyl, R3 and R4 independently of one another are C1 -C12 alkyl, C2 -C4 alkyl which is substituted by C1 -C4 alkoxy, --CN or --COO(C1 -C4 alkyl), allyl, cyclohexyl or benzyl, or R3 and R4 together are C4 -C6 alkylene, which can be interrupted by --O--or --N(R17)--, R11 is hydrogen, C1 -C4 alkyl, allyl, benzyl or C2 -C4 alkanoyl, R12 is C2 -C6 alkylene, R13, R14, R15 and R16 independently of one another are hydrogen or methyl, R17 is hydrogen, C1 -C.sub. 4 alkyl, benzyl, 2-hydroxyethyl or acetyl, R18 is hydrogen, C1 -C4 alkyl, 2-hydroxyethyl, 2-methoxyethyl, 2-allyloxyethyl, allyl, cyclohexyl, phenyl, benzyl or --Si(CH3)3, R19 is hydrogen, C1 -C12 alkyl, 2-hydroxyethyl, 2-methoxyethyl, phenyl, p-tolyl or benzyl, and R20 and R21 independently of one another are hydrogen, C1 -C12 alkyl, C2 -C6 alkoxyalkyl, acetyl, allyl or benzyl, or R20 and R21 together are C4 -C6 alkylene, which can be interrupted by --O--or --N(R17)--, and, in the case where R1 is allyl, R5 is not --OCH3, and in the case where R1 is benzyl and R2 is methyl or benzyl, R5 is not --OCH3 or --SCH3.
Particularly preferred compounds of the formula I are those in which Ar1 is a group of the formula IV in which R5 is a group --OR18, --SR19 or --N(R20)(R21), R6 is hydrogen, chlorine or C1 -C4 alkyl or has one of the meanings given for R5, R7 and R8 are hydrogen or chlorine, R9 is hydrogen or C1 -C4 alkyl, R1 is either (a) a radical of the formula --CH2 --C(R14)═CH(R15) or (b) a radical of the formula --CH2 -Ar2, in which Ar2 is a phenyl radical which is unsubstituted or substituted by halogen, C1 -C4 alkyl, CH3 S--, CH3 O-- or benzyl, R2 has one of the meanings given for R1 or is C1 -C4 alkyl, R3 and R4 independently of one another are C1 -C6 alkyl, 2-methoxyethyl, allyl or benzyl, or R3 and R4 together are tetramethylene, pentamethylene or 3-oxapentamethylene, R14 and R15 are hydrogen or methyl, R18 is C1 -C4 alkyl, 2-hydroxyethyl, 2-methoxyethyl or phenyl, R19 is C1 -C12 alkyl, 2-hydroxyethyl, 2-methoxyethyl, phenyl or p-tolyl and R20 and R21 are hydrogen, C1 -C4 alkyl, 2-methoxyethyl, acetyl or allyl, or R20 and R21 together are C4 -C5 -alkylene, alkylene, which can be interrupted by --O--or --N(CH3)--, and in the case where R1 is allyl, R5 is not --OCH3, and in the case where R1 is benzyl and R2 is methyl or benzyl, R5 is not --OCH3 or --SCH3.
Of these compounds, preferred compounds are those in which R5 is a group --SR19, R1 is a radical of the formula ##STR14## and either R7 and R8 are hydrogen or R6, R7, R8 and R9 are hydrogen, and those in which R1 is allyl.
Of the compounds of the formula I in which Ar1 is a group of the formula IV in which R5 is a group --N(R20)(R21), compounds which are preferred are those in which R7 and R8 are hydrogen, and those in which R6, R7, R8 and R9 are hydrogen, and those in which R1 is allyl or benzyl.
Preferred compounds of the formula I are moreover those in which Ar1 is a group of the formula IV in which R5 is hydrogen, halogen or C1 -C12 alkyl and R6, R7, R8 and R9 are hydrogen, R1 is allyl or benzyl, R2 is C1 -C6 alkyl, allyl or benzyl, R3 and R4 independently of one another are C1 -C12 alkyl, C2 -C4 alkyl which is substituted by C1 -C4 -alkoxy, --CN or --COO(C1 -C4 alkyl), allyl, cyclohexyl or benzyl, or R3 and R4 together are C4 -C6 alkylene, which can be interrupted by --O-- or --NR17)-- and R17 is hydrogen, C1 -C4 alkyl or 2-hydroxyethyl.
Examples of individual compounds of the formula I are:
1. 2-(dimethylamino)-2-ethyl-1-(4-morpholinophenyl)-4-penten-1-one
2. 2-(dimethylamino)-2-methyl-1-(4-morpholinophenyl)-4-penten-1-one
3. 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-propan-1-one
4. 4-morpholino-4-(4-morpholinobenzyl)-hepta-1,6-diene
5. 2-ethyl-2-morpholino-1-(4-morpholinophenyl)-4-penten-1-one
6. 2-benzyl-2-(dimethylamino)-1-[4-(dimethylamino)-phenyl]-butan-1-one
7. 4-dimethylamino-4-(4-dimethylaminobenzoyl)-hepta-1,6-diene
8. 4-(dimethylamino)-4-(4-morpholinobenzoyl)-hepta-1,6-diene
9. 2-(dimethylamino)-2-(4-dimethylaminophenyl)-2-ethyl-4-penten-1-one
10. 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-butan 1-one
11. 2-benzyl-2-(dimethylamino)-1-[4-(dimethylamino)-phenyl]-4-penten-1-one
12. 2-benzyl-1-[4-(dimethylamino)-phenyl]-2-(dimethylamino)-3-phenyl-propan-1-one
13. 2-ethyl-1-[4-(methylthio)-phenyl]-2-morpholino-4-penten-1-one
14. 4-[4-(methylthio)-benzoyl]-4-morpholino-hepta-1,6-diene
15. 4-(dimethylamino)-4-(4-methoxybenzoyl)-hepta-1,6-diene
16. 4-(4-methoxybenzoyl)-4-morpholino-hepta-1,6-diene
17. 1-(4-methoxyphenyl)-2-morpholino-2-phenyl-4-penten-1-one
18. 2-ethyl-1-(4-methoxyphenyl)-2-morpholino-4-penten-1-one
19. 2-benzyl-2-(dimethylamino)-1-[4-(methylthio)-phenyl]-butan-1-one
20. 2-(dimethylamino)-2-ethyl-1-[4-(methylthio)-phenyl]-4-penten-1-one
21. 2-benzyl-2-(dimethylamino)-1-[4-(methylthio)-phenyl]-4-penten-1-one
22. 4-(dimethylamino)-4-[4-(methylthio)-benzoyl]-1,6-heptadiene
23. 2-(dimethylamino)-3-(4-fluorophenyl)-2-methyl-1-[4-(methylthio)-phenyl]-propan-1-one
24. 3-(4-chlorophenyl)-2-(dimethylamino)-2-methyl-1-[4-(methylthio)-phenyl]-propan-1-one
25. 3-(2-chlorophenyl)-2-(dimethylamino)-2-methyl-1-[4-(methylthio)-phenyl]-propan-1-one
26. 3-(4-bromophenyl)-2-(dimethylamino)-2-methyl-1-[4-(methylthio)-phenyl]-propan-1-one
27. 2-ethyl-4-methyl-1-[4-(methylthio)-phenyl]-2-morpholino-4-penten 1-one
28. 2-ethyl-1-[4-(methylthio)-phenyl]-2-morpholino-4-hexen-1-one
29. 2-benzyl-1-[4-(methylthio)-phenyl]-2-morpholino-4-penten-1-one
30. 2-allyl-1-[4-(methylthio)-phenyl]-2-morpholino-hexan-1-one
31. 2-(dimethylamino)-1-[4-(methylthio)-phenyl]-2-methyl-3-(4-methyl-phenyl)-propan-1-one
32. 2-(dimethylamino)-1,3-bis-[4-(methylthio)-phenyl]-2-methyl-propan-1-one
33. 2-(dimethylamino)-1-[4-(methylthio)-phenyl]-2-methyl-3-(4-methoxy-phenyl)-propan-1-one
34. 1-[4-(melthio)-phenyl]-2-methyl-2-morpholino-4-penten-1-one
35. 2-(dimethylamino)-1-[4-(methylthio)-phenyl]-2-methyl-4-penten-1-one
36. 1-[4-(methylthio)-phenyl]-2-morpholino-2-phenyl-4-penten-1-one
37. 2-(dimethylamino)-1-[4-(methylthio)-phenyl]-2-phenyl-4-penten-1-one
38. 2-(dimethylamino)-1-[4-(methylthio)-phenyl]-2,3-diphenyl-propan-1-one
39. 2-methyl-2-morpholino-1-(4-morpholinophenyl)-4-penten-1-one
40. 2-benzyl-2-morpholino-1-(4-morpholinophenyl)-4-penten-1-one
41. 2-ethyl-2-morpholino-1-(4-morpholinophenyl)-4-penten-1-one
42. 1-[4-(dimethylamino)-phenyl]-2-methyl-2-morpholino-4-penten-1-one
43. 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-3-phenyl-propan-1-one
44. 4-[4-(dimethylamino)-benzoyl]-4-morpholino-hepta-1,6-diene
45. 2-(dimethylamino)-1-[4-(dimethylamino)-phenyl]-2-methyl-4-penten-1-one
46. 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-4-penten-1-one
47. 1-[4-(dimethylamino)-phenyl]-2-ethyl-4-methyl-2-morpholino-4-penten-1-one
48. 1-[4-(dimethylamino)-phenyl]-2-ethyl-2-morpholino-4-hexen-1-one
49. 2-ethyl-2-morpholino-1-(4-morpholinophenyl)-4-hexen-1-one
50. 2-ethyl-4-methyl-2-morpholino-1-(4-morpholinophenyl)-4-penten-1-one
51. 1-[4-(bis-(2-methoxyethyl)amino)-phenyl]-2-methyl-2-morpholino-4-penten-1-one
52. 1-[4-(dibutylamino)phenyl]-2-methyl-2-morpholino-4-penten-1-one
53. 2-methyl-1-[4-(4-methyl-piperazin-1-yl)-phenyl]-2-morpholino-4-penten-1-one
54. 2-benzyl-2-(dimethylamino)-1-(4-methoxyphenyl)-butan-1-one
55. 1-[4-(diethylamino)-phenyl]-2-methyl-2-morpholino-4-penten-1-one
56. 2-methyl-2-morpholino-1-[4-(pyrrolidin-1-yl)-phenyl]-4-penten-1-one
57. 2-benzyl-2-(dimethylamino)-1-(4-piperidinophenyl)-butan-1-one,
58. 2-ethyl-2-(dimethylamino)-1-(4-piperidinophenyl)-4-penten-1-one
59. 2-benzyl-1-[4-(diethylamino)phenyl]-2-ethyl-butan-1-one
60. 1-[4-(diethylamino)phenyl]-2-ethyl-4-penten-1-one
61. 2-benzyl-2-(dimethylamino)-1-[4-(2-hydroxyethylthio)-phenyl]-butan-1-one
62. 2-ethyl-1-[4-(2-hydroxyethylthio)-phenyl]-2-morpholino-4-penten-1-one
63. 1-[4-(diallylamino)-phenyl]-2-methyl-2-morpholino-4-penten-1-one
64. 3-(4-benzoylphenyl)-2-(dimethylamino)-2-methyl-1-[4-(methylthio)-phenyl]-propan-1-one
65. 2-(dimethylamino)-3-(3,4-dimethoxyphenyl)-2-methyl-1-phenyl-propan-1-one
66. 2-(dimethylamino)-3-(3,4-dimethoxyphenyl)-2-methyl-1-[4-(methyl-thio)-phenyl]-propan-1-one
67. 3-(4-benzoylphenyl)-2-(dimethylamino)-2-methyl-1-phenyl-propan-1-one
68. 2-benzyl-2-(dimethylamino)-1-(4-fluorophenyl)-butan-1-one
69. 4-(dimethylamino)-4-(4-fluorobenzoyl)-hepta-1,6-diene
70. 2-ethyl-2-morpholino-1-[4-(4-methylphenylsulfonyl)phenyl]-4-penten-1-one
71. 2-(dimethylamino)-2-ethyl-1-[4-(methylsulfonyl)phenyl]-4-penten-1-one
72. 2-benzyl-2-(dimethylamino)-1-[4-(methylphenylsulfonyl)phenyl]-butan-1-one
73. 2-benzyl-2-(dimethylamino)-1-[4-methylsulfonyl)phenyl]-butan-1-one
74. 1-(4-fluorophenyl)-2-methyl-2-morpholino-4-penten-1-one
75. 4-(4-fluorobenzoyl)-4-morpholino-hepta-1,6-diene
76. 2-benzyl-2-(dimethylamino)-1-(4-fluorophenyl)-4-penten-1-one
77. 2-benzyl-2-(dimethylamino)-1-(4-fluorophenyl)-3-phenyl-propan-1-one
78. 2-(dimethylamino)-2-ethyl-1-(4-fluorophenyl)-4-penten-1-one
79. 2-benzyl-1-(4-fluorophenyl)-2-morpholino-4-penten-1-one
80. 2-ethyl-1-(4-fluorophenyl)-2-morpholino-4-penten-1-one
81. 2-benzyl-2-(dimethylamino)-1-(4-fluorophenyl)-propan-1-one
82. 2-(dimethylamino)-1-(4-fluorophenyl)-2-methyl-4-penten-1-one
83. 2-benzyl-2-(dimethylamino)-1-(4-hydroxyphenyl)-butan-1-one
84. 2-benzyl-1-[4-(ethoxycarbonylmethyloxy)phenyl]-2-(dimethylamino)-butan-1-one
85. 2-benzyl-2-(dimethylamino)-1-[4-(2-hydroxyethyloxy)phenyl]-butan-1-one
86. 2-benzyl-1-(4-chlorophenyl)-2-(dimethylamino)-butan-1-one
87. 2-benzyl-1-(4-bromophenyl)-2-(dimethylamino)-butan-1-one
88. 1-(4-bromophenyl)-2-ethyl-2-morpholino-4-penten-1-one
89. 2-ethyl-1-(4-methoxyphenyl)-2-morpholino-3-penten-1-one
90. 2-(dimethylamino)-2-ethyl-1-(4-methoxyphenyl)-4-penten-1-one
91. 2-benzyl-1-[4-(dimethylamino)phenyl]-2-morpholino-4-penten-1-one
92. 2-benzyl-2-(dimethylamino)-1-[4-(dimethylamino)phenyl]-propan-1-one
93. 2-methyl-2-morpholino-1-phenyl-4-penten-1-one
94. 2-benzyl-2-morpholino-1-phenyl-4-penten-1-one
95. 2-(dimethylamino)-2-methyl-1-phenyl-4-penten-1-one
96. 2-benzyl-2-(dimethylamino)-1-phenyl-propan-1-one
97. 4-benzoyl-4-(dimethylamino)-hepta-1,6-diene
98. 2-benzyl-2-(dimethylamino)-1,3-diphenyl-propan-1-one
99. 2-benzyl-2-(dimethylamino)-1-phenyl-4-penten-1-one
100. 2-(dimethylamino)-2-ethyl-1-phenyl-4-penten-1-one
101. 2-benzyl-2-(dimethylamino)-1-phenyl-butan-1-one
102. 1,2-diphenyl-2-morpholino-4-penten-1-one
103. 3-(4-chlorophenyl)-2-(dimethylamino)-2-methyl-1-phenyl-propan-1-one
104. 3-(4-bromophenyl)-2-(dimethylamino)-2-methyl-1-phenyl-propan-1-one
105. 3-(2-chlorophenyl)-2-(dimethylamino)-2-methyl-1-phenyl-propan-1-one
106. 3-(3,4-dimethoxyphenyl)-2-(dimethylamino)-2-methyl-1-phenyl-propan-1-one
107. 2-(dimethylamino)-2-methyl-3-(4-methylphenyl)-1-phenyl-propan-1-one
108. 2-(dimethylamino)-2-methyl-3-[4-(methylthio)phenyl]-1-phenyl-propan-1-one
109. 2-(dimethylamino)-3-(4-fluorophenyl)-2-methyl-1-phenyl-propan-1-one
110. 2-(dimethylamino)-3-(4methoxy-phenyl)-2-methyl-1-phenyl-propan-1-one
111. 2-ethyl-1-(4-fluorophenyl)-4-methyl-2-morpholino-4-penten-1-one
112. 2-ethyl-1-(4-fluorophenyl)-5-methyl-2-morpholino-4-penten-1-one
113. 2-(benzylmethylamino)-2-ethyl-1-(4-morpholinophenyl)-4-penten-1-one
114. 2-(allylmethylamino)-2-ethyl-1-(4-morpholinophenyl)-4-penten-1-one
115. 2-benzyl-2-(benzylmethylamino)-1-(4-morpholinophenyl)-4-butan-1-one
116. 2-benzyl-2-(butylmethylamino)-1-(4-morpholinophenyl)-4-butan-1-one
117. 2-(butylmethylamino)-1-(4-morpholinophenyl)-4-penten-1-one
118. 1-(4-acetylaminophenyl)-2-benzyl-2-dimethylamino-butan-1-one
119. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-pentan-1-one
120. 2-allyl-2-dimethylamino-1-(4-morpholinophenyl)-pentan-1-one
121. 2-morpholino-1-[4-(2-methoxyethyloxy)phenyl]-2-methyl-4-penten-one
122. 4-morpholino-4-[4-(2-hydroxyethylthio)benzoyl]-5-methyl-1-hexene
123. 1-(4-bromophenyl)-2morpholino-2-methyl-4-penten-1-one
124. 4-(4-bromobenzoyl)-4morpholino-5-methyl-1-hexene
125. 1-(4-[2-hydroxyethylthio]phenyl)-2-methyl-2-morpholino-4-penten-1-one
126. 1-(4-[2-(allyloxy)-ethoxy]phenyl)-2-ethyl-2-morpholino-4-penten-1-one
127. 1-(4-[2-(allyloxy)-ethoxy]phenyl)-2-methyl-2morpholino-4-penten-1-one
128. 1-(4-[2-(methoxy)-ethoxy]phenyl)-2-ethyl-2-morpholino-4-penten-1-one
129. 2-benzyl-2-dimethylamino-1-[4-(2-methoxyethylamino)phenyl]-butan-1-one
130. 2-benzyl-2-dimethylamino-1-(4-methylaminophenyl)-butan-1-one
131. 2-benzyl-2-dimethylamino-1-[4-(N-acetylmethylamino)phenyl]-butan-1-one
132. 2-benzyl-2-diethylamino-1-(4-morpholino-phenyl)-butan-1-one
133. 2-diethylamino-2-ethyl-1-(4-morpholino-phenyl)-4-penten-1-one
140. 2-benzyl-2-(dimethylamino)-1-(3,5-dimethyl-4-methoxy-phenyl)-butan-1-one
141. 2-benzyl-1-(2,4-dichlorophenyl)-2-(dimethylamino)-butan-1-one
142. 2-(dimethylamino)-2-ethyl-1-(3.4-dichlorophenyl)-4-penten-1-one
143. 2-benzyl-1-(3,4-dichlorophenyl)-2-(dimethylamino)-butan-1-one
144. 1-(3-chloro-4-morpholino-phenyl)-2-(dimethylamino)-butan-1-one
145. 2-benzyl-1-(3-chloro-4-morpholino-phenyl)-2-(dimethylamino)-butan-1-one
146. 2-benzyl-2-dimethylamino-1-(4-dimethylamino-3-ethyl-phenyl)-butan-1-one
147. 2-benzyl-2-dimethylamino-1-(4-dimethylamino-2-methyl-phenyl)-butan-1-one
148. 9-butyl-3,6-di(2-benzyl-2-dimethylamino-butyryl)carbazole
149. 9-butyl-3,6-di(2-methyl-2-morpholino-4-penten-1-on-1-yl)-carbazole
150. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one-tri-fluoracetate
151. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one-p-toluenesulfonate
152. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one-camphorsulfonate
153. 4-(dimethylamino)-4-[4-(phenyloxy)-benzoyl]-hepta-1,6-diene
154. 2-benzyl-2-(dimethylamino)-1-(4-isopropyloxyphenyl)-4-penten-1-one
155. 1-(4-butyloxyphenyl)-2-ethyl-2-morpholino-4-penten-one
156. 1-(4-allyloxyphenyl)-2-benzyl-2-(dimethylamino)-butan-1-one
157. 2-methyl-2-morpholino-1-[4-(trimethylsilyloxy)-phenyl]-4-penten-1-one
158. 2-benzyl-2-(dimethylamino)-1-[4-((1,1,2-trimethylpropyl-dimethyl)-silyloxy)-phenyl]-butan-2-one
159. 2-ethyl-1-[4-(ethylthio)-phenyl]-2-morpholino-4-penten-1-one
160. 2-benzyl-1-[4-(butylthio)-phenyl]-2-(dimethylamino)-3-phenyl-propan-1-one
161. 1-[4-(isopropylthio)-phenyl]-2-methyl-2-morpholino-4-penten-1-one
162. 1-[4-(allylthio)-phenyl]-2-ethyl-2-morpholino-4-penten-1-one
163. 1-[4-(benzylthio)-phenyl]-2-benzyl-2-(dimethylamino)-propan-1-one
164. 2-benzyl-2-(dimethylamino)-1-(4-mercaptophenyl)-butan-1-one
165. 2-benzyl-1-[4-(cyclohexylthio)-phenyl]-2-(dimethylamino)-3-phenyl-propan-1-one
166. 2-ethyl-1-[4-(4-methylphenylthio)-phenyl]-2-morpholino-4-penten-1-one
167. 2-benzyl-2-(dimethylamino)-1-[4-(octylthio)-phenyl]-butan-1-one
168. 2-benzyl-1-[4-(chlorophenylthio)-phenyl]-2-(dimethylamino)-4-penten-1-one
169. 2-methyl-1-[4-(2-methoxycarbonylethylthio)-phenyl]-2-morpholino-4-penten-1-one
170. 1-[4-(butylsulfinyl)-phenyl]-2-(dimethylamino)-2-ethyl-4-penten-1-one
171. 1-[4-(benzenesulfonyl)-phenyl]-2-benzyl-2-(dimethylamino)-butan-1-one
172. 2-benzyl-2-(dimethylamino)-1-[4-(methylsulfinyl)-phenyl]-butan-1-one
173. 2-ethyl-1-[4-(4-methylphenylsulfonyl)-phenyl]-2-morpholino-4-penten-1-one
174. 1-(3,4-dimethoxyphenyl)-2-ethyl-2-morpholino-4-penten-1-one
175. 2-benzyl-1-(3,4-dimethoxyphenyl)-2-(dimethylamino)-butan-1-one
176. 4-(3,4-dimethoxybenzoyl)-4-(dimethylamino)-hepta-1,6-diene
177. 1-(1,3-benzodioxol-5-yl)-2-benzyl-2-(dimethylamino)-butan-1-one
178. 1-(1,3-benzodioxol-5-yl)-2methyl-2-morpholino-4-penten-1-one
179. 2-benzyl-2-(dimethylamino)-1-(3,4,5-trimethoxyphenyl)-butan-1-one
180. 1-(dibenzofuran-3-yl)-2-ethyl-2-morpholino-4-penten-1-one
181. 1-(4-benzoylphenyl)-2-benzyl-2-(dimethylamino)-propan-1-one
182. 2-[2-benzyl-2-(dimethylamino)-butanoyl]-fluorenone
183. 2-(2-methyl-2-morpholino-4-pentenoyl)-xanthone
184. 2-[2-allyl-2-(dimethylamino)-4-pentenoyl]-acridanone
185. 2-[2-benzyl-2-(dimethylamino)-butanoyl]-dibenzosuberone
186. 1-(N-butylcarbazol-3-yl)-2-ethyl-2-morpholino-4-penten-1-one
187. 2-benzyl-1-(N-butylcarbazol-3-yl)-2-(dimethylamino)-butan-1-one
188. 2-allyl-2-(dimethylamino)-1-(N-methylphenothiazin-2-yl)-4-penten-1-one
189. 2-benzyl-1-(N-butyl-phenoxazin-2-yl)-2-morpholino-propan-1-one
190. 2-benzyl-2-(dimethylamino)-1-(xanthen-2-yl)-butan-1-one
191. 1-(chroman-6-yl)-2-ethyl-2-morpholino-4-penten-1-one
192. 2-benzyl-2-(dimethylamino)-1-(N-methylindolin-5-yl)-propan-1-one
193. 1-(N-butylindolin-5-yl)-2-ethyl-2-morpholino-4-penten-1-one
194. 1-(5,10-dibutyl-5,10-dihydrophenazin-6-yl)-2-(dimethylamino)-4-penten-1-one
195. 2-benzyl-1-(1,4-dimethyl-1,2,3,4-tetrahydroquinoxalin-6-yl)-2-(dimethylamino)-butan-1-one
196. 1-(1,4-dibutyl-1,2,3,4-tetrahydroquinoxalin-6-yl)-2-ethyl-2-morpholino-4-penten-1-one
197. 2-benzyl-1-(2,3-dihydro-2,3-dimethyl-benzothiazol-5-yl)-2-(dimethylamino)-butan-1-one
198. 1-(2,3-dihydrobenzofuran-5->1)-2-methyl-2-morpholino-4-penten-1-one
199. 2-benzyl-1-(2,3-dihydrobenzofuran-5-yl)-2-(dimethylamino)-butan-2-one
200. 1-(4-aminophenyl)-2-benzyl-2-(dimethylamino)-butan-2-one
201. 1-[4-(butylamino)phenyl]-2-methyl-2-morpholino-4-penten-1-one
202. 2-benzyl-2-(dimethylamino)-1-[4-(isopropylamino)phenyl]-butan-1-one
203. 2-ethyl-1-(4-methoxyphenyl)-2-piperidino-4-penten-1-one
204. 2-methyl-2-(N-methylpiperazino)-1-[4-(N-methylpiperazino)phenyl]-4-penten-1-one
205. 2-benzyl-2-[di(2-methoxyethyl)-amino]-1-[4-(thiomethyl)phenyl]-butan-1-one
206. 2-(dibutylamino)-1-(4-methoxyphenyl)-2-methyl-4-penten-1-one
207. 1-[4-(dimethylamino)-phenyl]-2-ethyl-2-(methylphenylamino)-4-penten-1-one
208. 2-methyl-1-(methoxyphenyl)-2-oxazolidino-4-penten-1-one
209. 2-ethyl-1-(4-morpholinophenyl)-2-piperidino-4-penten-1-one
200. 2-methyl-2-piperidino-1-(4-piperidinophenyl)-4-penten-1-one
211. 2-ethyl-1-[4-(methylthio)phenyl]-2-piperidino-4-penten-1-one
212. 2-benzyl-2-(dibutylamino)-1-[4-(methylthio)phenyl]-butan-1-one
213. 2-(dibutylamino)-2-methyl-1-[4-(dimethylamino)phenyl]-4-penten-1-one
214. 2-benzyl-2-(dibutylamino)-1-(4-morpholinophenyl)-butan-1-one
215. 2-(dimethylamino)-1-[4-(dimethylamino)-phenyl]-2-[(1-cyclo-hexenyl)-methyl]-butan-1-one
216. 2-(dimethylamino)-2-(2-cyclopentenyl)-1-(4-morpholinophenyl)-propan-1-one
217. 2-ethyl-2-(4-morpholinophenyl)--N-methyl-1,2,3,6-tetrahydropyridine
218. 2-(dimethylamino)-1-[4-(dimethylamino)-phenyl]-2,4,5-trimethyl-4-hexen-1-one
219. 2-(dimethylamino)-1-[4-(dimethylamino)-phenyl]-2-(2-pinen-10-yl)-butan-1-one
220. 2-benzyl-2-(dimethylamino)-1-[4-(2,6-dimethylmorpholin-4-yl)-phenyl]-butan-1-one
221. 2-ethyl-2-(2.6-dimethylmorpholin-4-yl)-1-[4-(2,6-dimethylmorpholin-4-yl)phenyl]-4-penten-1-one
222. 1-[4-(dimethylamino)phenyl]-2-ethyl-2-(2,6-dimethylmorpholin-4-yl)-4-penten-1-one
223. 1-[4-(2,6-dimethylmorpholin-4-yl)phenyl]-2-methyl-2-morpholino-4-penten-1-one
224. 2-ethyl-1-[4-(2-hydroxyethoxy)phenyl]-2-morpholino-4-penten-1-one
225. 1-[4-(2-methoxyethyloxy)phenyl]-2-methyl-2-morpholino-4-penten-1-one
226. 1-[4-(2-hydroxyethylthio)phenyl]-2-morpholino-2-propyl-4-penten-1-one
227. 2-benzyl-2-(dimethylamino)-1-[4-(2-methoxyethylthio)phenyl]-butan-1-one
228. 2-(dimethylamino)-2-isopropyl-1-(4-morpholino-phenyl)-4-penten-1-one
229. 2-benzyl-1-(3,5-dichlorophenyl)-2-(dimethylamino)-butan-1-one
230. 1-(3,5-dichloro-4-methoxyphenyl)-2-methyl-2-morpholino-4-penten-1-one
231. 2-(diallylamino)-2-ethyl-1-(4-morpholinophenyl)-4-penten-1-one
232. 1-[4-(dimethylamino)phenyl]-2-methyl-2-(pyrrolidin-1-yl)-4-penten-1-one
233. 2-benzyl-2-(dimethylamino)-1-(4-methylphenyl)butan-1-one
234. 1-(4-dodecylphenyl)-2-ethyl-2-morpholino-4-penten-1-one
235. 2-methyl-1-(4-methylphenyl)-2-morpholino-4-penten-1-one
236. Dodecylbenzenesulfonate of 2-ethyl-2-morpholino-1-(4-morpholinophenyl)-4-penten-1-one
237. Dodecylbenzenesulfonate of 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-butan-1-one.
238. 2-dimethylamino-2-(4-dodecylbenzyl)-1-(4-morpholinophenyl)-butan-1-one
239. 2-(4-ethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one
240. 2-dimethylamino-2-(4-isopropylbenzyl)-1-(4-morpholinophenyl)-butan-1-one
241. 2-dimethylamino-1-(4-dimethylaminophenyl)-1-(4methylbenzyl)-butan-1-one
242. 2-dimethylamino-2-(4-hydroxymethylbenzyl)-1-(4-morpholinophenyl)-butan-1-one
243. 2-(4-[acetoxyethyl]benzyl)-2-dimethylamino-1-(4-morpholino-phenyl)-butan-1-one
244. 2-dimethylamino-2-(4-[2-(2-methoxyethoxy)-ethyloxy]benzyl)-1-(4-morpholinophenyl)-butan-1-one
245. 2-dimethylamino-2-(4-[2-(2-[2-methoxyethoxy]-ethoxycarbonyl)-ethyl]benzyl)-1-(4-morpholin phenyl)-butan-1-one
246. 2-(4-[2-bromoethyl]benzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one
247. 2-(4-[2-diethylaminoethyl]benzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one
248. 2-dimethylamino-1-(4-dimethylaminophenyl)-2-(4-dodecylbenzyl)-butan-1-one
249. 2-dimethylamino-1-(4-dimethylaminophenyl)-2-(4-isopropylbenzyl)-butan-1-one
250. 2-dimethylamino-2-(3,4-dimethylbenzyl)-1-(4-morpholinophenyl)-butan-1-one
251. 2-dimethylamino-2-[4-(2-(2-methoxyethoxy)-ethoxycarbonyl)benzyl]-1-(4-morpholinophenyl)-butan-1-one
264. 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one
265. 2-(4-butylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)-butan-1-one
266. 2-(dimethylamino)-2-(4-isobutylbenzyl)-1-(4-morpholinophenyl)-butan-1-one
267. 2-benzyl-2-(dimethylamino)-1-(4-[3-methoxypropylamino]phenyl)-butan-1-one
268. 1-(4-[N-acetyl-3-methoxypropylamino]phenyl)-2-benzyl-2-(dimethylamino)-butan-1-one
269. 2-benzyl-2-(di[2-methoxyethyl]amino)-1-(4-morpholinophenyl)-butan-1-one
270. 2-ethyl-2-(di[2-methoxyethyl]amino)-1-(4-morpholinophenyl)-4-penten-1-one
271. 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-hexan-1-one
272. 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-heptan-1-one
273. 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-octan-1-one
274. 2-benzyl-2-(dimethylamino)-4,5,5-trimethyl-1-(4-morpholinophenyl)-hexan-1-one
275. 2-(dimethylamino)-2-(4-methoxybenzyl)-1-(4-morpholinophenyl)-butan-1-one
276. 2-(4-butoxybenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)-butan-1-one
277. 2-(dimethylamino)-2-(4-[2-hydroxyethoxy]-benzyl)-1-(4-morpholino-phenyl)-butan-1-one
278. 2-(dimethylamino)-2-(4-[2-methoxyethoxy]-benzyl)-1-(4-morpholinophenyl)-butan-1-one
279. 2-(dimethylamino)-2-(4-isopropylbenzyl)-1-(4-morpholinophenyl)-butan-1-one
280. 2-(dimethylamino)-2-(4-dodecylbenzyl)-1-(4-morpholinophenyl)-octan-1-one
281. 2-(dimethylamino)-2-(2-isopropylbenzyl)-1-(4-morpholinophenyl)-pentan-1-one
282. 2-(dimethylamino)-1-(4-(dimethylamino)phenyl-2-(4-[2methoxy]-benzyl)-heptan-1-one
283. 2-(butylmethylamino)-2-(4-isopropylbenzyl)-1-(4-morpholinophenyl)-butan-1-one
284. 2-(4-isobutylbenzyl)-2-(butylmethylamino)-1-(4-morpholinophenyl)-pentan-1-one
285. 2-(4-methylbenzyl)-2-(dioctylamino)-1-(4-morpholinophenyl)-hexan-1-one
286. 2-(4-butoxybenzyl)-2-(butylmethylamino)-1-(4-morpholinophenyl)-pentan-1-one and
287. 2-(4-butylbenzyl)-2-(butylmethylamino)-1-(4-morpholinophenyl)-hexan-1-one.
Examples of individual compounds of the formula II are:
252. N,N'-bis[1-ethyl-1-(4-morpholinobenzoyl)-3-butenyl]-piperazine
253. N,N'-bis[1-allyl-1-(4-(dimethylamino)-benzoyl)-3-butenyl]-piperazine
254. N,N-bis[1-benzyl-1-(4-methoxybenzoyl)-propanyl]-methylamine
255. N,N'-bis[1-ethyl-1-(4-(methylthio)-benzoyl)-butenyl]-hexamethylenediamine.
256. N,N'-bis[1-benzyl-1-(4-morpholinobenzoyl)-propan-1-yl]--N,N'-dimethyl-3,6,9,12-tetraoxa-tetradecamethylenediamine
Examples of individual compounds of the formula III are:
257. 1,10-bis[4-dimethylamino)-phenyl]-2,9-diallyl-2,9-dimorpholinodecane-1,10-dione
258. 1,6-bis[4-(methylthio)-phenyl]-2,4-bis(dimethylamino)-2,4-dibenzylhexane-1,6-dione
259. 1,4-bis[2-(dimethylamino)-2-(4-morpholinobenzoyl)-4-pentenyl]-benzene
260. 1,4-bis[2-(dimethylamino)-2-(4-methoxybenzoyl)-3-phenylpropanyl]-benzene.
261. 1,4-bis[2-(dimethylamino)-2-(4-morpholinobenzoyl)-butyl)benzene
262. 3,8-bis(dimethylamino)-3,8-bis(4-morpholinobenzoyl)-dec-5-ene
263. 3,8-bis(dimethylamino)-5,6-dimethylidene-3,8-bis(4-morpholinobenzoyl)-decane
In most of these compounds, R1 --or R1 and R2 --is a substituent of the allyl or benzyl type. The synthesis of such compounds usually includes C-allylation or C-benzylation. The amino group --NR3 R4 is preferably introduced before the allylation/benzylation. The synthesis is then carried out in the following sequence of reaction steps: ##STR15##
The starting ketones are known compounds which can be prepared, for example, by a Friedel-Crafts reaction. Reaction steps 1 and 2 are known reactions which are described in more detail, for example, in EP-A-3,002. The two reactions can be carried out one after the other without isolating the bromoketone.
Reaction 3 is described in detail below. In the case of C-allylation, it can proceed via the enol allyl ether as an intermediate in the sense of Claisen rearrangement. In the case of C-benzylation or C-allylation, this can proceed via a quaternary benzylammonium salt or allylammonium salt as an intermediate in the sense of a Stevens rearrangement. In both cases, however, the intermediate is not isolated. If both R1 and R2 are allyl or benzyl groups, the above reaction sequence is started with an aryl methyl ketone Ar1 --CO--CH3 and reaction 3 is carried out twice, using R1 Hal once and R2 Hal once.
If the aromatic radical Ar1 carries substituents which are not inert towards reactions 1, 2 or 3, the synthesis is carried out with an auxiliary substituent which is converted into the desired substituent in a subsequent step 4. For example, the syntheses can be carried out with a nitroaryl compound and this can then be reduced to the corresponding amino compound. Alternatively, the synthesis is started with a halogenoaryl compound and the halogen is then replaced by --OR18, --SR19 or --NR20 R21 in a nucleophilic replacement reaction. A group --SR19 can then be oxidized to --SO--R19 or --SO2 --R19.
For synthesis of compounds of the formula II, a primary amine R11 NH2 or a secondary diamine R11 --NH--R12 --NH--R11 or piperazine is used in reaction stage 2 and reaction 3) and if appropriate 4) are subsequently carried out.
For synthesis of compounds of the formula III, a bis-aryl ketone of the formula
Ar1 --CO--CH2 --Y--CH2 --CO--Ar1
is used as the starting substance and is subjected to reactions 1, 2 and 3.
If R1 is a substituent of the vinyl type, such compounds can be prepared from the corresponding allyl compounds by a catalyzed double bond isomerization. If R1 is a substituent of the formula ##STR16## this is introduced in the same way as an allyl radical using a halogen compound of the formula ##STR17##
Another possibility for the synthesis of compounds of the formula I is reaction of an α-aminonitrile with an aryl-lithium compound and subsequent hydrolysis: ##STR18## Such reactions have been described, for example, by Cromwell and Hess in J. Am. Chem. Soc. 83, 1237 (1961). The α-aminonitriles are accessible directly by Strecker synthesis from R1 --CO--R2, or can be prepared by allylation or benzylation of an α-aminonitrile NC--CHR2 --NR3 R4. The allylation of α-aminonitriles is described, for example, by T. S. Stevens in J. Chem. Soc. 1930, 2119.
Compounds of the formula I in which R1 and R2 together with the C atom to which they are bonded form a cycloalkene ring can be prepared analogously by reaction of aryl-lithium compounds with the corresponding cyclic nitriles. The cyclic nitriles can be obtained by cycloaddition of α-aminoacrylonitriles onto 1,3-dienes, such as has been described, for example, by Brucher and Stella in Tetrahedron 41, 875 (1985): ##STR19##
Finally, there is also the possibility of reacting the α-bromoketones with a tertiary allyl- or benzylamine and subjecting the quaternary salt formed to a Stevens rearrangement: ##STR20## According to the invention, the compounds of the formula I, II and III can be used as photoinitiators for photopolymerization of ethylenically unsaturated compounds or mixtures containing such compounds. The unsaturated compounds can contain one or more olefinic double bonds. They can be of low molecular weight (monomeric) or of higher molecular weight (oligomeric). Examples of monomers with a double bond are alkyl acrylates or methacrylates or hydroxyalkyl acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate and methyl or ethyl methacrylate. Further examples of these are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, vinyl esters, such as vinyl acetate, vinyl ethers, such as isobutyl vinyl ether, styrene, alkyl- and halogenostyrenes, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.
Examples of monomers with several double bonds are the diacrylates of ethylene glycol, propylene glycol, neopentylglycol, hexamethylene glycol or bisphenol A, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate and tris-(2-acryloyloxyethyl) isocyanurate.
Examples of higher molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated polyethers, acrylated polyurethanes and acrylated polyesters. Further examples of unsaturated oligomers are unsaturated polyester resins, which are usually prepared from maleic acid, phthalic acid and one or more diols and have molecular weights of about 500 to 3000. Such unsaturated oligomers can also be called prepolymers.
Two-component mixtures of a prepolymer with a polyunsaturated monomer or three-component mixtures which additionally also contain a monounsaturated monomer are frequently used. The prepolymer here is primarily decisive for the properties of the lacquer film, and by varying it the expert can influence the properties of the cured film. The polyunsaturated monomer functions as crosslinking agents which render the lacquer film insoluble. The monounsaturated monomer functions as reactive diluents, with the aid of which the viscosity is reduced without having to use a solvent.
Such two- and three-component systems based on a prepolymer are used both for printing inks and for lacquers, photoresists or other photocurable compositions. One-component systems based on photocurable prepolymers are frequently also used as binders for printing inks.
Unsaturated polyester resins are usually used in two-component systems together with a monounsaturated monomer, preferably with styrene. Specific one-component systems, for example polymaleimides, polychalcones or polyimides, such as are described in DE-OS 2,308,830, are often used for photoresists.
The unsaturated compounds can also be used as a mixture with non-photo-polymerizable film-forming components. These can be, for example, polymers which dry by physical means and solutions thereof in organic solvents, for example nitrocellulose or cellulose acetobutyrate. They can also be, however, resins which can be cured chemically or thermosetting resins, for example polyisocyanates, polyepoxides or melamine resins. The joint use of thermosetting resins is of importance for use in so-called hybrid systems which are photopolymerized in a first stage and crosslinked by thermal after-treatment in a second stage.
The photopolymerizable mixtures can contain various additives in addition to the photoinitiator. Examples of these are thermal inhibitors for the purpose of preventing premature polymerization, for example hydroquinone or sterically hindered phenols. Copper compounds, phosphorus compounds, quaternary ammonium compounds or hydroxylamine derivatives, for example, can be used to increase the storage stability in the dark. Paraffin or similar waxy substances which migrate to the surface at the start of polymerization can be added for the purpose of excluding atmospheric oxygen during the polymerization. UV absorbers, for example those of the benzotriazole, benzophenone or oxalanilide type, can be added in a small amount as light stabilizers. The addition of light stabilizers which do not absorb UV light, for example sterically hindered amines (HALS), is even better.
In certain cases, it may be advantageous to use mixtures of two or more of the photoinitiators according to the invention. Mixtures with known photoinitiators can, of course, also be used, for example mixtures with benzophenone, acetophenone derivatives, benzoin ethers or benzil ketals.
Amines, for example triethanolamine, N-methyl-diethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone, can be added to accelerate the photopolymerization. The effect of the amines can be intensified by addition of aromatic ketones of the benzophenone type.
Acceleration of the photopolymerization can furthermore be effected by addition of photosensitizers which shift or extend the spectral sensitivity. These are, in particular, aromatic carbonyl compounds, for example derivatives of benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin, and 3-(aroylmethylene)-thiazolines.
The effectiveness of the photoinitiators according to the invention can be increased by addition of titanocene derivatives with fluoroorganic radicals, such as are described in EP-A-122,223 and 186,626, for example in an amount of 1-20%. Examples of such titanocenes are bis(methylcyclopentadienyl)-bis(2,3,6-trifluorophenyl)-titanium, bis-(cyclopentadienyl)-bis-(4-dibutylamino-2,3,5,6-tetrafluorophenyl)-titanium, bis(methylcyclopentadienyl)-2-(trifluoromethyl)phenyltitanium isocyanate, bis(cyclopentadienyl)-2-(trifluoromethyl)phenyltitanium trifluoroacetate and bis-(methylcyclopentadienyl)-bis(4-decyloxy-2,3,5,6-tetrafluorophenyl)-titanium. Liquid α-aminoketones are especially suitable for these mixtures.
The photocurable compositions according to the invention can be used for various purposes. Their use in pigmented or coloured systems, for example for printing inks, for photographic reproduction processes, for image recording processes and for producing relief forms, is of particular importance.
Another important field of use are paints, which can be pigmented or non-pigmented. The mixtures are particularly useful in white lacquers, by which is understood paints pigmented with TiO2. Other fields of use are radiation-curing of photoresists, photocrosslinking of silver-free films and production of printing plates. Another use is for external paint films which subsequently harden on their surface in daylight.
The photoinitiators are advantageously used in amounts of 0.1 to 20% by weight, preferably about 0.5 to 5% by weight, based on the photopolymerizable composition, for the fields of use listed.
The polymerization is carried out by the known methods of photopolymerization by irradiation with light rich in short-wavelength radiation. Suitable light sources are, for example, medium-pressure, high-pressure and low-pressure mercury lamps, superactinic tubular lamps and metal halide lamps or lasers with emission maxima in the range between 250 and 450 nm. In the case of combination with photosensitizers or ferrocene derivatives, light of longer wavelengths or laser beams up to 600 nm can also be used.
The preparation and use of the photoinitiators according to the invention are described in more detail in the following examples. In these, parts are parts by weight, percentages are percentages by weight and the temperature is given in degrees Celsius.
240 g (0.98 mol) of 1-(4-fluorophenyl)-2-bromobutan-1-one (prepared by bromination of 4-fluorobutyrophenone by the method described in EP-A-3,002) are dissolved in 250 ml of diethyl ether. This solution is slowly added dropwise to a mixture of 265 g (5.87 mol) of dimethylamine in 1250 ml of diethyl ether at 0�. After the mixture has been stirred at 0� for 12 hours, the excess dimethylamine is removed at room temperature by blowing through N2 and the suspension is poured onto water. The ether phase is washed with water and dried over MgSO4. After filtration and evaporation of the solution, 202.8 g of crude product remain as a colourless oil, which is used without further purification for the subsequent reaction.
The NMR spectrum (CDCl3) of the crude product agrees with the structure given: 7.8-8.23 (m, 2H); 6.8-7.3 (m, 2H); 3.75 (d�d, 1 H); 2.3 (s, 6H); 1.46-2.3 (m, 2H); 0.83 (t, 3H).
100 g of 1)-2-dimethylamino-butan-1-one (crude product from A) are dissolved in 330 ml of acetonitrile. 98.1 g (0.57 mol) of benzyl bromide are slowly added dropwise, with stirring. After the mixture has been stirred at room temperature for 12 hours, the solvent is distilled off in vacuo. The residue is dissolved in 500 ml of water and the solution is heated to 55�-60�. 113 g of a 34% NaOH solution (0.96 mol) are added dropwise at this temperature and the mixture is subsequently stirred for 30 minutes.
After cooling, the reaction mixture is extracted with diethyl ether and the ether phase is dried over MgSO4 and evaporated. 117.1 g of crude product which is used without further purification for the subsequent reaction remain. The NMR spectrum of the crude product agrees with the structure given.
NMR (CDCl3)-- δ(ppm): 8.1-8.53 (m, 2H); 6.76-7.5 (m, 7,H); 3.16 (s, 2H); 2.33 (s, 6H); 1.53-2.2 (m, 2H); 0.65 (t, 3H).
A stirred autoclave is filled with 50 g (0.167 mol) of 1-(4-fluorophenyl)-2-dimethylamino-2-benzylbutan-1-one (crude product from B), 300 ml of dimethylformamide and 23.1 g (0.167 mol) of potassium carbonate. 22.6 g (0.5 mol) of dimethylamine are then added under pressure (3-4 bar). The mixture is heated to 100� and stirred at this temperature for 24 hours.
After cooling, the excess dimethylamine is evaporated off and the reaction mixture is poured onto ice/water and extracted with diethyl ether. The ether phase is washed with water, dried over MgSO4 and evaporated in vacuo. The liquid residue is purified by means of medium-pressure chromatography, ethyl acetate/hexane 15:85 being used as the eluting agent.
44 g of crude product which crystallizes from ethanol are obtained.
Melting point 77�-80�.
______________________________________Analysis Calculated C 77.74% H 8.70% N 8.63% Found C 77.59% H 8.71% N 8.62%______________________________________
A dispersion of 12.4 g (0.51 mol) of sodium hydride in 50 ml of hexane is diluted with 300 ml of dimethylformamide (DMF). A solution of 117.7 g (0.47 mol) of 1-(4-fluorophenyl)-2-morpholinobutan-1-one in 250 ml of DMF is added dropwise to this suspension in the course of 2 hours, with stirring.
70.8 g (0.58 mol) of allyl bromide are added at room temperature in the course of one hour and the reaction mixture is heated at 110� until no further starting material can be detected in a sample by thin-layer chromatography. After cooling, the reaction mixture is poured onto ice/water and extracted with diethyl ether. The ether phase is dried over MgSO4 and evaporated in vacuo.
127 g of an oily crude product which can be used without further purification for the subsequent reaction are obtained as the residue. The NMR spectrum of the crude product corresponds to the structure given.
NMR (CDCl3), δ(ppm): 8.46 (d�d, 2H); 7 (t, 2H); 4.8-6.5 (m, 3H); 3.5-3.9 (m, 4H); 2.4-3.2 (m, 6H); 1.7-2.3 (m, 2H); 0.75 (t, 3H).
608.7 g (2.03 mol) of 1-(4-fluorophenyl)-2-dimethylamino-2-benzyl-butan-1-one (Example 1, B), 354.2 g (4.06 mol) of morpholine, 562 g (4.06 mol) of K2 CO3 and 2000 ml of dimethylsulfoxide are heated at 160� for 12 hours, with stirring. After this time, a sample no longer shows any starting ketone in a thin-layer chromatogram. The reaction solution is cooled to room temperature, poured onto ice and extracted with methylene chloride. The organic phase is dried over MgSO4, filtered and evaporated. The oily residue crystallizes from ethanol. The product melts at 111�-119�.
______________________________________Analysis Calculated C 75.37% H 8.25% N 7.64% Found C 75.40% H 8.27% N 7.63%______________________________________
118 g (0.65 mol) of α-dimethylamino-4-fluoroacetophenone are dissolved in 350 ml of acetonitrile. 94.5 g (0.78 mol) of allyl bromide are slowly added dropwise to this solution at about 25� and the reaction mixture is stirred at room temperature for 12 hours. The solvent is evaporated off in vacuo and the solid residue is dissolved in warm water (about 60�). After slow addition of 169 ml of 30% aqueous NaOH (1.27 mol) and cooling to room temperature, the mixture is extracted with diethyl ether. The ether phase is dried and evaporated. The residue obtained is crude 2-dimethylamino-1-(4-fluorophenyl)-4-penten-1-one in the form of an oil, which is used without further purification for the subsequent reaction. The NMR spectrum of the product is in good agreement with the structure given: 7.83-8.23 m (2H, HB), 6.9-7.26 m (2H, HA), 4.76-6.0 m (3H, Holefin), 3.96 d�d (1H, J=6 Hz, J=8.5 Hz, Hc), 2.2-2.7 m (2H, HD), 2.3s (6H, HE).
131 g (0.59 mol) of the crude product from F) in 350 ml of acetonitrile and 85.9 g (0.71 mol) of allyl bromide are reacted as in F). Neutralization of the reaction mixture is carried out with 160 ml of 30% NaOH (1.2 mol). The crude product is likewise isolated as in F). The reaction product is a yellowish oil which can be used without further purification for the next stage (amination of the nucleus).
NMR (CDCl3): 8.53-8.1 m (2H, HB), 7.2-6.7 m (2H, HA), 6.1-4.7 m (6H, Holefin), 2.8-2.5 m (4H, Hallyl), 2.4s (6H, N--CH3)
A suspension of 100 g (0.6 mol) of carbazole in 200 ml of toluene is heated under reflux, with stirring. After cooling to 95�, first 26.8 g (0.12 mol) of triethylbenzylammonium chloride and then a solution of 169.8 g of KOH in 180 ml of water are added. The temperature thereby drops to 65�. 205.6 g (1.5 mol) of butyl bromide are now added in the course of 5 minutes, with vigorous stirring, whereupon the temperature rises to 92�. The mixture is kept under reflux for a further 10 minutes, all the carbazole dissolving. The aqueous phase is then removed. .The toluene phase is washed with a little water, dried over Na2 CO3 and evaporated in vacuo. The oily residue is dissolved in 300 ml of warm hexane and the solution is clarified. On cooling, the product crystallizes in beige-coloured crystals of melting point 50�-52�.
46.9 g (0.44 mol) of butyryl chloride are added dropwise to a suspension of 93.3 g (0.7 mol) of AlCl3 in 100 ml of methylene chloride in the course of 30 minutes, while stirring and cooling to -10� to -5�. A solution of 22.3 g (0.1 mol) of N-butylcarbazole in 50 ml of CH2 Cl2 is then added dropwise at -10� to -5� in the course of 2 hours. The suspension is stirred at 0� to 20� for 16 hours and then poured onto ice. The emulsion formed is extracted twice with CHCl3 and the extract is washed with water, dried over MgSO4 and evaporated. The crude 3,6-dibutyryl-9-butyl-9H-carbazole is re-crystallized from 80 ml of ethanol. The resulting crystals have a melting point of 107�-109�.
3,6-Dipropionyl-9-butyl-9H-carbazole, which has a melting point of 142�-144� , is obtained in an analogous manner from 81.4 g of propionyl chloride and 44.7 g of N-butylcarbazole.
The products listed in the following tables are prepared analogously to the general Preparation Examples A-I.
TABLE 1 ##STR26## Compound Physical Analysis No. R5 R1 R2 NR3 R4 properties C H N S 1 ##STR27## Allyl Ethyl N(CH3)2 m.p. 58-61� calc.found 72.1172.08 8 .85% 8.73% 2 ##STR28## Allyl Methyl N(CH3)2 oil calc.found 71.4971.56 8.678.64 9 9.25%.04% 3 ##STR29## Benzyl Methyl N(CH3)2 m.p. 90-92� calc.found 74.9775.09 8.018.09 7.95% 7.71% 4 ##STR30## Allyl Allyl ##STR31## oil calc.found 71.3271.24 8.168.12 7.56% 7.57% 5 ##STR32## Allyl Ethyl ##STR33## oil calc.found 70.3669.87 8.438.41 7.81% 7.64% 6 (CH3)2 N Benzyl Ethyl N(CH3)2 m.p. 77-80� calc. 77.74 8.70 8.63% found 77.59 8.71 8.62% 7 (CH3)2 N Allyl Allyl N(CH3)2 oil calc. 75.48 9.15 9.78% found 75.48 9.25 9.48% 8 ##STR34## Allyl Allyl N(CH3)2 m.p. 65-67� calc.found 73.1473.05 8.598.51 8.59% 8.51% 9 (CH3)2 N Allyl Ethyl N(CH3)2 m.p. 34-37� calc. 74.41 9.55 10.21% found 74.29 9.55 10.23% 10 ##STR35## Benzyl Ethyl N(CH3)2 m.p. 110-119� calc.found 75.3775.3 8 8.258.32 7.64% 7.62% 11 (CH.sub. 3)2 N Benzyl Allyl N(CH3)2 m.p. 68-70� calc. 78.53 8.39 8.33% found 78.54 8.38 8.10% 12 (CH3)2 N Benzyl Benzyl N(CH3)2 m.p. 132-133� calc. 80.79 7.82 7.25% found 80.71 7.91 7.21% 13 CH3 S Allyl Ethyl ##STR36## oil calc.found 67.6867.43 7.897.81 4.38% 4.22% 14 CH3 S Allyl Allyl ##STR37## oil calc.found 68.8568.83 7.617.56 4.23% 4.17% 15 CH3 O Allyl Allyl N(CH3)2 oil calc. 74.69 8.48 5.12% found 74.54 8.48 5.04% 16 CH3 O Allyl Allyl ##STR38## oil calc.found 72.3572.51 7.998.09 4.44% 4.14% 17 CH3 O Allyl Phenyl ##STR39## m.p. 84-86� calc.found 75.1974.97 7.177.14 3.99% 3.91% 18 CH3 O Allyl Ethyl ##STR40## oil calc.found 71.2671.19 8.308.44 4.62% 4.57% 19 CH3 S Benzyl Ethyl N(CH3)2 oil calc. 73.35 7.69 4.28 9.79% found 73.47 7.69 4.12 9.61% 20 CH3 S Allyl Ethyl N(CH3)2 oil calc. 69.27 8.35 5.05 11.55% found 69.24 8.41 5.00 11.41% 21 CH3 S Allyl Benzyl N(CH3)2 oil calc. 74.29 7.42 4.12 9.44% found 74.22 7.44 3.92 9.26% 22 CH3 S Allyl Allyl N(CH3)2 oil calc. 70.55 8.01 4.82 11.08% found 70.58 8.00 4.70 10.93% 23 CH3 S 4-Fluorobenzyl Methyl N(CH3)2 oil calc. 68.85 6.69 4.22 9.67% found 68.89 6.84 4.06 9.57% 24 CH3 S 4-Chlorobenzyl Methyl N(CH3)2 m.p. 69-70� calc. 65.60 6.37 4.03 9.22% found 65.30 6.34 3.92 9.25% 25 CH3 S 2-Chlorobenzyl Methyl N(CH3)2 oil calc. 65.59 6.37 4.03 9.22% found 65.98 6.51 3.97 9.09% 26 CH3 S 4-Bromobenzyl Methyl N(CH3)2 oil calc. 58.16 5.65 3.57 8.17% found 58.35 5.71 3.44 7.99% 27 CH3 S Methallyl Ethyl ##STR41## oil calc.found 68.4368.41 8.168.28 4.20 3.93 9.61% 9.53% 28 CH3 S 2-Butenyl Ethyl ##STR42## oil calc.found 68.4368.46 8.168.20 4.20 4.08 9.61% 9.53% 29 CH3 S Allyl Benzyl ##STR43## oil calc.found 72.4072.51 7.137.31 3.67 3.52 8.40% 8.25% 30 CH3 S Allyl Butyl ##STR44## oil calc.found 69.1268.98 8.418.29 4.03 3.80 9.23% 9.26% 31 CH3 S 4-Methylbenzyl Methyl N(CH3)2 m.p. 74-75� calc. 73.35 7.69 4.28 9.79% found 72.84 7.72 4.29 9.66% 32 CH3 S 4-Methylthiobenzyl Methyl N(CH3)2 oil calc. 66.81 7.01 3.89 17.83% found 66.70 7.17 3.69 17.41% 33 CH3 S 4-Methoxybenzyl Methyl N(CH3)2 oil calc. 69.93 7.34 4.08 9.33% found 69.50 7.38 3.84 9.49% 34 CH3 S Allyl Methyl ##STR45## oil calc.found 66.8566.92 7.597.60 4.59 4.53 10.50%10.50% 35 CH3 S Allyl Methyl N(CH3)2 oil calc. 68.40 8.04 5.32 12.17% found 68.09 8.07 5.32 12.16% 36 CH3 S Allyl Phenyl ##STR46## m.p. 97-99� calc.found 71.9071.76 6.867.00 3.81 3.70 8.72% 8.74% 37 CH3 S Allyl Phenyl N(CH3)2 oil calc. 73.81 7.12 4.30 9.85% found 73.36 7.10 4.05 9.78% 38 CH3 S Benzyl Phenyl N(CH3)2 m.p. 142-143� calc. 76.76 6.71 3.73 8.54% found 76.95 6.75 3.77 8.50% 39 ##STR47## Allyl Methyl ##STR48## oil calc. found 69.7469.43 8.198.33 8.13% 7.87% 40 ##STR49## Allyl Benzyl ##STR50## m.p. 150� calc.found 74.2674.22 7.677.66 6.66% 6.68% 41 (CH3)2 N Allyl Ethyl ##STR51## oil calc.found 72.1272.14 8.928.95 8.85% 8.62% 42 (CH3)2 N Allyl Methyl ##STR52## waxy calc.found 71.4971.51 8.678.72 9.26% 9.12% 43 ##STR53## Benzyl Benzyl N(CH3)2 m.p. 177-178� calc.found 78.4778.57 7.537.59 6.54% 6.47% 44 (CH3)2 N Allyl Allyl ##STR54## oil calc.found 73.1473.42 8.598.84 8.53% 7.83% 45 (CH3)2 N Allyl Methyl N(CH3)2 oil calc. 73.81 9.29 10.76% found 73.41 9.06 9.65% 46 ##STR55## Allyl Benzyl N(CH3)2 m.p. 91-93� calc.found 76.1676.27 7 .998.04 7.40% 7.12% 47 (CH3)2 N Methallyl Ethyl ##STR56## m.p. 79-84� calc.found 72.6972.57 9.159.24 8.48% 8.49% 48 (CH3)2 N 2-Butenyl Ethyl ##STR57## oil calc.found 72.6972.12 9.159.17 8.48% 7.99% 49 ##STR58## 2-Butenyl Ethyl ##STR59## oil calc.found 70.9370.61 8.668.75 7.52% 6.93% 50 ##STR60## Methallyl Ethyl ##STR61## oil calc.found 70.9370.42 8.668.71 7.52% 7.11% 51 (CH3 OCH2 CH2)2 N Allyl Methyl ##STR62## oil calc.found 67.6667.81 8.788.76 7.17% 7.25% 52 (C4 H9)2 N Allyl Methyl ##STR63## oil calc.found 74.5774.62 9.919.87 7.25% 7.30% 53 ##STR64## Allyl Methyl ##STR65## oil calc.found 70.5570.27 8.748.81 11.75%11.64% 54 CH3 O Benzyl Ethyl N(CH3)2 oil calc. 77.13 8.09 4.50% found 77.09 8.15 4.47% 55 (C2 H5)2 N Allyl Methyl ##STR66## oil calc.found 72.6972.66 9.159.15 8.48% 8.24% 56 ##STR67## Allyl Methyl ##STR68## m.p. 98-99� calc.found 73.1473.10 8.598.59 8.53% 8.48% 57 ##STR69## Benzyl Ethyl N(CH3)2 m.p. 76-81� calc.found 79.0878.96 8 .858.79 7.68% 7.60% 58 ##STR70## Allyl Ethyl N(CH3)2 oil calc.found 76.3976.40 9.629.50 8.90% 8 .74% 59 (C2 H5)2 N Benzyl Ethyl N(CH3)2 oil calc. 78.36 9.15 7.95% found 77.79 9.08 7.14% 60 (C2 H5)2 N Allyl Ethyl N(CH3)2 oil calc. 75.45 9.99 9.26% found 75.35 9.80 8.70% 61 HOCH2 CH2 S Benzyl Ethyl N(CH3)2 oil calc. 70.55 7.61 3.92 8.97% found 70.18 7.51 3.71 8.95% 62 HOCH2 CH2 S Allyl Ethyl ##STR71## oil calc.found 65.3064.54 7.797.76 4.013.79 9.17% 9.35% 63 (CH2CHCH 2)2 N Allyl Methyl ##STR72## oil 64 CH3 S 4-Benzoylbenzyl Methyl N(CH3)2 m.p. 135-136� calc. 74.79 6.52 3.35 7.68% found 74.53 6.56 3.24 7.55% 65 H 3,4-Dimethoxybenzyl Methyl N(CH3)2 m.p. 116-117� calc. 73.36 7.69 4.27% found 73.03 7.73 4.11% 66 CH3 S 3,4-Dimethoxybenzyl Methyl N(CH3)2 oil calc. 67.53 7.29 3.75 8.58% found 67.41 7.32 4.03 8.99% 67 H 4-Benzoylbenzyl Methyl N(CH3)2 m.p. 106-108� calc. 80.83 6.78 3.77% found 80.22 6.75 3.79% 68 F Benzyl Ethyl N (CH3)2 m.p. 62-65� calc. 76.22 7.41 4.68% found 76.07 7.40 4.60% 69 F Allyl Allyl N(CH3)2 oil 70 ##STR73## Allyl Ethyl ##STR74## vitreous calc.found 67.4266.98 6.487.10 3.28 3.12 7.50% 7.51% 71 CH3 SO2 Allyl Ethyl N(CH3)2 m.p. 74-75� calc. 62.11 7.49 4.53 10.36% found 62.03 7.48 4.50 10.27% 72 ##STR75## Benzyl Ethyl N(CH3)2 m.p. 107-108� calc.found 71.6971.4 6 6.716.68 3.22 3.16 7.36% 7.39% 73 CH3 SO2 Benzyl Ethyl N(CH3)2 vitreous calc. 66.82 7.01 3.90 8.92% found 66.74 7.01 3.81 8.94% 74 F Allyl Methyl ##STR76## oil calc.found 69.2969.02 7.277.47 5.05% 4.86% 75 F Allyl Allyl ##STR77## oil calc.found 71.2671.19 7.317.25 4.62% 4.50% 76 F Allyl Benzyl N(CH3)2 oil 77 F Benzyl Benzyl N(CH3)2 oil 78 F Allyl Ethyl N(CH3)2 oil 79 F Allyl Benzyl ##STR78## oil 80 F Allyl Ethyl ##STR79## oil 81 F Benzyl Methyl N(CH3)2 oil 82 F Allyl Methyl N(CH.sub. 3)2 oil 83 HO Benzyl Ethyl N(CH3)2 m.p. 110-119� 84 C2 H5 OOCCH2 O Benzyl Ethyl N(CH3)2 oil calc. 72.04 7.62 3.65% found 72.00 7.62 3.57% 85 HOCH2 CH2 O Benzyl Ethyl N(CH3)2 oil calc. 73.87 7.97 4.10% found 73.83 8.09 3.82% 86 Cl Benzyl Ethyl N(CH3)2 m.p. 67-69� calc. 72.25 7.02 4.43% found 72.32 7.03 4.34% 87 Br Benzyl Ethyl N(CH3)2 m.p. 53-55� calc. 63.34 6.15 3.89% found 63.22 6.19 3.87% 88 Br Allyl Ethyl ##STR80## oil calc.found 57.9658.42 6.306.42 3.98% 3.94% 89 CH3 O l-Propenyl Ethyl ##STR81## oil calc.found 71.2671.31 8.318.31 4.62% 4.42% 90 CH3 O Allyl Ethyl N(CH3)2 oil 91 (CH3)2 N Allyl Benzyl ##STR82## oil calc.found 76.1676.17 7.997.98 7.40% 7.13% 92 (CH3)2 N Benzyl Methyl N(CH3)2 m.p. 107-108� 93 H Allyl Methyl ##STR83## liquid calc.found 74.1074.28 8.168.37 5.40% 5.31% 94 H Allyl Benzyl ##STR84## oil calc.found 78.7778.82 7.51 7.76 4.11% 3.73% 95 H Allyl Methyl N(CH3)2 liquid calc. 77.40 8.80 6.45% found 77.34 8.79 6.41% 96 H Benzyl Methyl N(CH3)2 liquid calc. 80.86 7.92 5.24% found 80.80 8.06 5.17% 97 H Allyl Allyl N(CH3)2 oil calc. 79.97 8.70 5.76% found 78.77 8.75 5.64% 98 H Benzyl Benzyl N(CH3)2 oil 99 H Allyl Benzyl N(CH3)2 oil calc. 81.87 7.90 4.77% found 81.70 7.84 4.65% 100 H Allyl Ethyl N(CH3)2 liquid calc. 77.88 9.15 6.05% found 77.85 9.17 6.01% 101 H Benzyl Ethyl N(CH3)2 oil calc. 81.10 8.24 4.98%found 81.14 8.45 4.93% 102 H Allyl Phenyl ##STR85## m.p. 87-88� calc.found 78.4778.17 7.217.10 4.36% 4.32% 103 H 4-Chlorobenzyl Methyl N(CH3)2 m.p. 86-87� calc. 71.63 6.68 4.64% found 71.58 6.67 4.62% 104 H 4-Bromobenzyl Methyl N(CH3)2 m.p. 101-102� calc. 62.43 5.82 4.04% found 62.35 5.86 3.96% 105 H 2-Chlorobenzyl Methyl N(CH3)2 oil calc. 71.63 6.68 4.64% found 71.12 6.66 4.35% 106 H 3,4-Dimethoxybenzyl Methyl N(CH3)2 m.p. 116-117.de gree. calc. 73.36 7.69 4.27% found 73.03 7.69 4.11% 107 H 4-Methylbenzyl Methyl N(CH3)2 oil calc. 81.10 8.24 4.98% found 80.57 8.23 4.94% 108 H 4-Methylthiobenzyl Methyl N(CH3)2 oil calc. 72.80 7.40 4.47% found 72.70 7.39 4.34% 109 H 4-Fluorobenzyl Methyl N(CH3)2 oil calc. 75.76 7.06 4.91% found 75.82 7.09 4.74% 110 H 4-Methoxybenzyl Methyl N(CH3)2 oil calc. 76.74 7.80 4.70% found 76.39 7.78 4.51% 111 F Methallyl Ethyl ##STR86## oil 112 F 2-Butenyl Ethyl ##STR87## oil 113 ##STR88## Allyl Ethyl N(CH3)(Benzyl) oil calc.found 76.4976.58 8.228.30 7.14% 6.81% 114 ##STR89## Allyl Ethyl N(CH3)(Allyl) oil calc.found 73.6573.68 8.838.82 8.18% 7.90% 115 ##STR90## Benzyl Ethyl N(CH3)(Benzyl) m.p. 60-65� calc.found 78.7078.5 9 7.747.87 6.33% 6.66% 116 ##STR91## Benzyl Ethyl N(CH3)(C4 H9) oil calc.found 76.4376.31 8 8.88.83 6.86% 6.73% 117 ##STR92## Allyl Ethyl N(CH3)(C4 H9) oil calc.found 73.7073.60 9.569.56 7.81% 7.66% 118 CH3 CONH Benzyl Ethyl N(CH3)2 glass 119 ##STR93## Benzyl Propyl N(CH3)2 glass calc.found 75.7576.08 8.488.54 7.36% 6.96% 120 ##STR94## Allyl Propyl N(CH3)2 m.p. 62-64� calc.found 72.6972.51 9 .158.97 8.48% 8.53% 121 CH3 OCH2 CH2 O Allyl Methyl ##STR95## oil calc.found 68.4468.26 8.168.24 4.20% 3.97% 122 HOCH2 CH2 S Allyl Isopropyl ##STR96## oil 123 Br Allyl Methyl ##STR97## oil 124 Br Allyl Isopropyl ##STR98## oil 125 HOCH2 CH2 S Allyl Methyl ##STR99## oil calc.found 64.4564.78 7.517.48 4.18 3.92 9.56% 9.63% 126 CH2CHCH 2 OCH2 CH2 O Allyl Ethyl ##STR100## oil calc.found 70.7570.75 8.378.25 3.75% 3.76% 127 CH2CHCH 2 OCH2 CH2 O Allyl Methyl ##STR101## oil 128 CH3 OCH2 CH2 O Allyl Ethyl ##STR102## oil calc.found 69.1469.23 8.418.34 4.03% 3.93% 129 CH3 OCH2 CH2 NH Benzyl Ethyl N(CH3)2 oil 130 CH3 NH Benzyl Ethyl N(CH3)2 oil 131 ##STR103## Benzyl Ethyl N(CH3)2 oil 132 ##STR104## Benzyl Ethyl N(C2 H5)2 m.p. 76-79� calc.found 76.1075.83 8.698.64 7.10% 7.09% 133 ##STR105## Allyl Ethyl N(C2 H5)2 oil calc.found 73.22 73.03 9.369.40 8.13% 7.64% 186 ##STR106## Benzyl Ethyl N(CH3)2 m.p. 103-105� C. calc.found 76.1075.80 8.688.75 7.10% 7.07% 240 ##STR107## 4-Isobutylbenzyl Ethyl N(CH3)2 m.p. 136-137� C. calc.found 76.4376.26 8.888.83 6.86% 6.71% 246 ##STR108## 4-(2-Bromoethyl)benzyl Ethyl N(CH3)2 resin calc.found 63.4263.13 7.037.28 5.92% 5.54% 264 ##STR109## 4-Methylbenzyl Ethyl N(CH3)2 m.p. 75-76� C. calc.found 7 5.7575.61 8.488.53 7.36% 7.26% 265 ##STR110## 4-Butylbenzyl Ethyl N(CH3)2 resin calc.found 76.7476.58 9.069.12 6.63% 6.45% 266 ##STR111## 4-Isobutylbenzyl Ethyl N(CH3)2 m.p. 77-80� C. calc.found 76.7476.60 9.069.10 6.63% 6.62% 267 CH3 O(CH2)3 NH Benzyl Ethyl N(CH3)2 oil calc. 74.96 8.57 7.60% found 75.39 8.52 7.40% 268 ##STR112## Benzyl Ethyl N(CH3)2 oil calc.found 73.1473.07 8.358.07 6.82% 6.77% 269 ##STR113## Benzyl Ethyl N(CH2 CH2 OCH3)2 oil calc.found 71.3471.11 8.438.64 6.16% 5.96% 270 ##STR114## Allyl Ethyl N(CH2 CH2 OCH3)2 oil calc.found 68.2967.91 8.979.21 6.92% 6.75%
TABLE 2__________________________________________________________________________ ##STR115##Compound Physical AnalysisNo. R5 R6 R8 R9 R1 R2 NR3 R4 properties C H N__________________________________________________________________________140 CH3 O CH3 H CH3 Benzyl Ethyl N(CH3)2 m.p. 68-70� calc. 77.84 8.61 4.13% found 77.71 8.63 3.93%141 Cl H Cl H Benzyl Ethyl N(CH3)2 oil calc. 65.15 6.04 4.00% found 65.07 5.93 3.95%142 Cl Cl H H Allyl Ethyl N(CH3)2 oil calc. 60.01 6.38 4.67% found 59.95 6.39 4.80%143 Cl Cl H H Benzyl Ethyl N(CH3)2 oil calc. 65.15 6.04 4.00% found 65.19 6.23 3.86%144 ##STR116## Cl H H Allyl Ethyl N(CH3)2 oil calc. found 65.04 64.40 7.76 7.82 7.98% 7.72%145 ##STR117## Cl H H Benzyl Ethyl N(CH3)2 m.p. 110-111�146 (CH3)2 N H H C2 H5 Benzyl Ethyl N(CH3)2 oil147 (CH3)2 N H CH3 H Benzyl Ethyl N(CH3)2 m.p. 101-103� calc. 78.06 8.93 8.28% found 77.97 8.92 8.22%__________________________________________________________________________
TABLE 3__________________________________________________________________________ ##STR118##Compound PhysicalNo. R1 R2 NR3 R4 R17 property C H N__________________________________________________________________________148 Benzyl Ethyl N(CH3)2 C4 H9 glass calc. 80.08 8.16 6.67% found 80.24 7.40 6.41%149 Allyl Methyl ##STR119## C4 H9 glass calc. found 73.81 73.66 8.09 8.05 7.17% 6.87%__________________________________________________________________________
TABLE 4__________________________________________________________________________Salts ##STR120##Compound Melting AnalysisNo. A point C H N__________________________________________________________________________150 CF3 COO 55-56� calc. 62.49 6.50 5.83% found 62.18 6.64 5.54%151 ##STR121## 90-95� calc. found 66.89 66.76 7.11 7.38 5.20% 4.78%152 ##STR122## 95-105� calc. found 66.19 65.57 7.74 8.04 4.68% 4.38%__________________________________________________________________________
A blue printing ink is prepared in accordance with the following formulation:
62 parts of Setalin� AP 565 (urethane acrylate resin from Synthese, Holland),
15 parts of 4,4'-di-(β-acryloyloxyethoxy)-2,2-diphenylpropane (Ebecryl� 150, UCB, Belgium) and
23 parts of Irgalithblau� GLSM (Ciba-Geigy AG, Basle).
The mixture is homogenized on a 3-roll mill and ground down to a particle size of <5 μm.
In each case 5 g of this printing ink are mixed homogeneously with the desired amount of photoinitiator on a plate grinding machine under a pressure of 180 kg/m2, while cooling with water. Samples with 3% and 6% of photoinitiator--based on the printing ink--are prepared.
Offset prints are made from these printing inks on 4�20 cm strips of art printing paper using a specimen printing apparatus (Prufbau, FR Germany). The printing conditions are: amount of printing ink applied: 1.5 g/m2, pressing pressure (line pressure): 25 kp/cm, printing speed: 1 m/second.
A printing roller with a metallic surface(aluminium) is used here.
The printed samples are cured in a UV irradiation apparatus from PPG using two lamps of 80 W/cm each. The irradiation time is varied by varying the rate of transportation of the sample.
The surface drying of the printing ink is tested by the so-called transfer test immediately after the irradiation. White paper is thereby pressed onto the printed sample under a line pressure of 25 kp/cm. If the paper remains colourless, the test has been passed. If visible amounts of colour are transferred to the test strips, this is an indication that the surface of the sample has not cured sufficiently.
The maximum rate of transportation at which the transfer test was still passed is shown in Table 5.
To test for complete curing of the printing ink, offset prints are likewise produced as described above, but printing rollers with a rubber surface are used and the metallic side of aluminum-coated strips of paper are printed.
The irradiation is carried out as described above. Complete curing is tested in a REL complete curing tester immediately after the irradiation. In this, an aluminium cylinder over which fabric is stretched is placed on the printed sample and rotated once around its own axis under a pressure of 220 g/cm2 in the course of 10 seconds. If visible damage is thereby caused to the sample, the printing ink has not completely cured sufficiently. The maximum rate of transportation at which the REL test was still passed is given in the tables.
TABLE 5______________________________________ Concen- Transfer REL TestPhotoinitiator tration Test (m/min) (m/min)______________________________________Compound No. 1 3% >170 150 6% >170 >170Compound No. 2 3% >170 130 6% >170 >170Compound No. 3 3% >170 140 6% >170 >170Compound No. 4 3% >170 130 6% >170 >170Compound No. 5 3% >170 120 6% >170 >170Compound No. 6 3% >170 160 6% >170 >170Compound No. 7 3% >170 130 6% >170 >170Compound No. 8 3% >170 150 6% >170 >170Compound No. 9 3% >170 130 6% >170 >170Compound No. 10 3% >170 130 6% >170 160Compound No. 11 3% >170 130 6% >170 160Compound No. 39 3% 140 80 6% >170 140Compound No. 40 3% 110 70 6% 140 70Compound No. 41 3% >170 110 6% >170 150Compound No. 42 3% 110 60 6% >170 90Compound No. 44 3% 110 70 6% >170 110Compound No. 45 3% >170 110 6% >170 160Compound No. 46 3% >170 120 6% >170 160Compound No. 47 3% >170 50Compound No. 48 3% >170 110Compound No. 51 3% 70 50 6% >170 110Compound No. 53 3% 120 60 6% >170 130Compound No. 63 3% 80 40 6% >170 80Compound No. 91 3% 110 70 6% >170 70Compound No. 92 3% >170 100 6% >170 120Compound No. 118 3% 140 100Compound No. 119 3% 160 80Compound No. 120 3% 170 150Compound No. 121 3% 120 90Compound No. 125 3% 130 100Compound No. 148 3% 120 80Compound No. 149 3% 170 110______________________________________
A white lacquer is prepared in accordance with the following formulation:
17.6 g of Ebecryl� 593 (polyester acrylate resin from UCB, Belgium),
11.8 g of N-vinylpyrrolidone,
19.6 g of titanium dioxide RTC-2 (titanium dioxide from Tioxide, England),
19.6 g of Sachtolith� HDS (lithopone from Sachtleben Chemie, FRG),
11.8 g of trimethylolpropane trisacrylate and
19.6 g of Setalux� UV 2276 (acrylated epoxy resin based on bisphenol A, Kunstharzfabrik Synthese, Holland).
The above components are ground down to a particle size of not more than 5 μm together with 125 g of glass beads (diameter 4 mm) in a 250 ml glass bottle for at least 24 hours.
The stock paste thus obtained is divided into portions, each portion is mixed with in each case 2% of the photoinitiators shown in Table 6 by stirring at 60� C. and the mixtures are ground again with glass beads for 16 hours.
The white lacquers thus prepared are applied in a thickness of 70 μm to glass plates using a doctor blade. The samples are exposed on the one hand in a PPG irradiation apparatus with a 80 W/cm lamp and on the other hand in an irradiation apparatus from Fusion Systems (USA) using a D lamp, in each case in one passage. The rate of passage of the samples through the irradiation apparatus is thereby increased continuously until adequate curing no longer occurs. The maximum rate at which a lacquer film which is still wipe-proof forms is shown in Table 6 as "curing rate".
TABLE 6______________________________________Photoinitiator Curing rate (m/minute)(in each case 2%) PPG apparatus 80 W Fusion D lamp______________________________________Compound No. 1 60 130Compound No. 3 50 170Compound No. 4 50 110Compound No. 6 140 >200Compound No. 7 80 >200Compound No. 8 70 150Compound No. 12 50 120Compound No. 14 70 --Compound No. 15 50 --______________________________________
The procedure is as in Example 6. However, in addition to the 2% of photoinitiator, 0.5% (based on the lacquer) of isopropylthioxanthone is also added as a sensitizer. A noticeable increase in the curing rate thereby occurs. The results are shown in Table 7.
TABLE 7______________________________________ Photoinitiator Curing rate (m/minute)(in each case 2%) Sensitizer PPG apparatus Fusion D lamp______________________________________Compound No. 1 -- 60 130 0.5% 130 180Compound No. 3 -- 50 170 0.5% 100 >200Compound No. 4 -- 50 110 0.5% 80 160Compound No. 6 -- 140 >200 0.5% 170 >200Compound No. 7 -- 80 >200 0.5% 170 >200Compound No. 8 -- 70 150 0.5% 120 >200Compound No. 12 -- 50 120 0.5% 110 >200______________________________________
A photocurable black offset printing ink is mixed with in each case 3% of the photoinitiators shown in Table 8 and paper laminated with aluminium foil is printed with the ink in an application amount of 1.5 g/m2, the procedure being as in Example 5. Curing is also carried out as described in Example 5 in the PPG apparatus with two lamps of 80 Watt. The curing is checked byt eh transfer test--as described in Example 5. Table 8 indicates the maximum rate of transportation in the irradiation apparatus at which the transfer test is still just passed.
TABLE 8______________________________________ Curing ratePhotoinitiator PPG apparatus (m/min)______________________________________Compound No. 6 120Compound No. 8 130Compound No. 9 130Compound No. 10 110______________________________________
A mixture of
______________________________________ 37.64 g pentaerythritol trisacrylate 10.76 g hexamethoxymethylmelamine (Cymel � 301, Cyanamid Corp.) 47.30 g of a thermoplastic carboxylated polyacrylate (Carboset � 525, Goodrich Corp.) and 4.30 g of polyvinylpyrrolidone100.00 g______________________________________
is dissolved in a mixture of 319 g methylene chloride and 30 g methanol. To this solution are added 0.5 g Irgalithgreen� GLN (Ciba-Geigy AG) and compound 10 as photoinitiator in the amounts indicated in table 9.
The viscous solution is applied to aluminium sheets in a thickness of 200 μm. After drying for 15 minutes at 60� the thickness is about 45 μm. The sample is covered with a polyester sheet (76 μm). An optical 21 step wedge (Stouffer wedge) is placed on the sheet and fixed by vacuum. The sample is irradiated for 20 seconds through the wedge with a 5 kW lamp at a distance of 30 cm. Afterwards the sheet is removed and the sample is developed in an ultrasonics bath. The developer employed is a solution of 15 g of Na2 SiO3 �9H2 O, 0.16 g of KOH, 3 g of polyethylene glycol 6000 and 0.5 g of levulinic acid in 1000 g of water. After being briefly dried at room temperature, the samples are assessed. Table 9 indicates the highest step which is completely reproduced and has a non tacky surface. The higher the step, the more sensitive is the system.
TABLE 9______________________________________Initiator Highest step______________________________________0.1% of compound No. 10 100.5% of compound No. 10 141.0% of compound No. 10 16______________________________________
88.6 parts of a butadiene/styrene copolymer (Cariflex� TR 1107, Shell Chemie) are plastisized on a calander at 140� . Then 11 parts of hexanediol diacrylate, 0.3 part of a phenolic antioxidant (Topano� OC, ICI Comp.), 0.01 part of Sudan Black B and 0.4 part of compound 10 are admixed at 100� and the mixture is homogenized at this temperature.
Plates of 2 mm thickness are pressed from this mixture between two polyester sheets. The back of the plates is irradiated through the sheet in a BASF-Nyloprint irradiation device with 40 W lamps. The sheet on the face of the plate is replaced by a test negative and this side is exposed for 6 minutes through this negative.
The exposed sample is developed in a brushing bath with a mixture of 4 parts of tetrachloroethylene and 1 part of butanol, while washing out the soluble parts. After drying for 60 minutes at 80� the second sheet is removed and the printing plate is immersed successively in a 0.4 % aqueous bromine solution and a 1.5 % solution of Na2 S2 O3 /Na2 CO3 followed by rinsing with water.
Finally, each side is irradiated for a further 6 minutes. All parts of the test negative are reproduced clearly. The depth of the indentations is 34 μm, the hight of the relief is 450 μm.
|Cited Patent
|Filing date
|Publication date
|Oct 12, 1971
|Apr 16, 1974
|Continental Can Co
|Photopolymerizable polyester compositions
|Dec 18, 1978
|Mar 9, 1982
|Ciba-Geigy Corporation
|Use of aromatic-aliphatic ketones as photo sensitizers
|Feb 13, 1984
|Dec 17, 1985
|Ciba Geigy Corporation
|Photocurable colored compositions employing alpha-amino phenone initiator
|Feb 22, 1983
|Apr 15, 1986
|Ciba-Geigy Corporation
|Ketone with morpholino and s-phenyl groups as photoinitiator in pigmented coating
|Aug 9, 1984
|Apr 24, 1985
|Ciba-Geigy Ag
|Photocurable compositions
|Citing Patent
|Filing date
|Publication date
|May 14, 1992
|Nov 8, 1994
|Nippon Kayaku Kabushiki Kaisha
|Photopolymerizable composition for color filter and color filter prepared therefrom
|Apr 5, 1995
|Jul 30, 1996
|Ciba-Geigy Corporation
|Photopolymerizable compositions
|Jun 6, 1995
|Sep 10, 1996
|Ciba-Geigy Corporation
|α-aminoacetophenones as photoinitiators
|Apr 22, 1996
|Jul 8, 1997
|Tokyo Ohka Kogyo, K.K.
|Process for the production of printing plates
|Nov 21, 1996
|Sep 16, 1997
|Minnesota Mining And Manufacturing Company
|Coatable compositions abrasive articles made therefrom, and methods of making and using same
|Apr 21, 1997
|Aug 18, 1998
|Ciba Specialty Chemicals Corporation
|Phenyl alkyl ketone substituted by cyclic amine and a process for the preparation thereof
|Jun 1, 1998
|Nov 2, 1999
|Ciba Specialty Chemical Corporation
|Phenyl alkyl ketone substituted by cyclic amine and a process for the preparation thereof
|Dec 1, 1997
|Feb 8, 2000
|Ciba Specialty Chemicals Corporation
|α-aminoacetophenone photoinitiators
|Dec 5, 1997
|May 2, 2000
|Ciba Specialty Chemicals Corporation
|Photogeneration of amines from α-aminoacetophenones
|Jun 10, 1999
|Feb 20, 2001
|Ciba Specialty Chemcials Corporation
|Phenyl alkyl ketone substituted by cyclic amine and a process for the preparation thereof
|Dec 18, 1995
|Mar 20, 2001
|Novartis Ag
|Functionalized photoinitiators, derivatives and macromers therefrom and their use
|Jun 3, 1999
|Aug 21, 2001
|Kimberly-Clark Worldwide, Inc.
|Photoinitiators and applications therefor
|Jan 15, 1998
|Aug 21, 2001
|Ciba Specialty Chemicals Corp.
|Photoactivatable nitrogen-containing bases based on α-amino ketones
|Feb 24, 2000
|Dec 18, 2001
|Kimberly-Clark Worldwide, Inc.
|Printing apparatus and applications therefor
|May 12, 2000
|Apr 9, 2002
|Kimberly-Clark Worldwide, Inc.
|Subphthalocyanine colorants, ink compositions, and method of making the same
|Jan 19, 2000
|Apr 9, 2002
|Kimberly-Clark Worldwide, Inc.
|Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
|Jun 13, 2001
|Jun 25, 2002
|Ciba Specialty Chemicals Corporation
|Photoactivatable nitrogen-containing bases based on alpha-amino ketones
|Jun 19, 2001
|Nov 26, 2002
|Kimberly-Clark Worldwide, Inc.
|Zinc-complex photoinitiators and applications therefor
|Jan 12, 2001
|Feb 25, 2003
|Kimberly-Clark Worldwide, Inc.
|Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
|Sep 7, 2000
|Apr 22, 2003
|Ciba Specialty Chemical Corporation
|Photoactivatable nitrogen-containing bases based on α-ammonium ketones, iminium ketones or amidinium ketones and aryl borates
|Apr 27, 2000
|Jan 6, 2004
|Ciba Specialty Chemicals Corporation
|Photoinitiators and their applications
|Jul 18, 2002
|Jul 24, 2007
|Ciba Specialty Chemicals Corporation
|Photosensitive resin composition
|Oct 17, 2003
|Nov 6, 2007
|Ciba Specialty Chemicals Corporation
|Storage stability of photoinitiators
|Jun 13, 2007
|Sep 16, 2008
|Ciba Specialty Chemicals Corporation
|Photosensitive resin composition
|Jun 13, 2007
|Jul 7, 2009
|Ciba Specialty Chemicals Corporation
|Photosensitive resin composition
|Oct 20, 2006
|Apr 26, 2011
|Dai Nippon Printing Co., Ltd.
|Photo radical generator, photo sensitive resin composition and article
|Jan 30, 2008
|Dec 13, 2011
|Fujifilm Corporation
|Ink set for inkjet recording and inkjet recording method
|Aug 11, 2008
|Jul 24, 2012
|Seiko Epson Corporation
|Photocurable ink composition and inkjet recording method
|Sep 30, 2010
|Jul 9, 2013
|Seiko Epson Corporation
|Inkjet-recording non-aqueous ink composition, inkjet recording method, and recorded matter
|Jul 10, 2012
|Aug 27, 2013
|Seiko Epson Corporation
|Ink set, ink container, inkjet recording method, recording device, and recorded matter
|Jan 28, 2011
|Sep 3, 2013
|Seiko Epson Corporation
|Aqueous ink composition, ink jet recording method, and recorded matter
|Mar 29, 2006
|Sep 10, 2013
|Seiko Epson Corporation
|Ink composition
|May 18, 2007
|Dec 10, 2013
|Mannkind Corporation
|Intracellular kinase inhibitors
|Jan 28, 2011
|Dec 24, 2013
|Seiko Epson Corporation
|Aqueous ink composition, ink jet recording method and recorded material
|Aug 3, 2011
|Mar 18, 2014
|Seiko Epson Corporation
|Ink composition, two-pack curing ink composition set, and recording method and recorded matter using these
|Mar 3, 2008
|Nov 25, 2014
|Seiko Epson Corporation
|Ink set, ink-jet recording method, and recorded material
|Feb 27, 2009
|May 19, 2015
|Seiko Epson Corporation
|Method of forming opaque layer, recording process, ink set, ink cartridge, and recording apparatus
|Dec 3, 2013
|Oct 27, 2015
|Seiko Epson Corporation
|Ink composition, two-pack curing ink composition set, and recording method and recorded matter using these
|Oct 14, 2014
|Apr 11, 2017
|Seiko Epson Corporation
|Ink set, ink-jet recording method, and recorded material
|May 27, 2009
|Apr 18, 2017
|Basf Se
|Photoinitiator mixtures
|Apr 8, 2003
|Apr 8, 2004
|Chiu Chingfan Chris
|Novel morpholinoketone derivatives, and preparation process and uses of the same
|Jul 18, 2002
|Sep 30, 2004
|Hisatoshi Kura
|Photosensitive resin composition
|Oct 17, 2003
|May 11, 2006
|Thomas Ulrich
|Storage stability of photoinitiators
|Jun 13, 2007
|Oct 25, 2007
|Hisatoshi Kura
|Photosensitive resin composition
|Jun 13, 2007
|Nov 8, 2007
|Hisatoshi Kura
|Photosensitive resin composition
|Jan 30, 2008
|Jul 31, 2008
|Fujifilm Corporation
|Ink set for inkjet recording and inkjet recording method
|Aug 11, 2008
|Apr 30, 2009
|Seiko Epson Corporation
|Photocurable ink composition, ink cartridge, inkjet recording method and recorded matter
|Aug 11, 2008
|Aug 20, 2009
|Seiko Epson Corporation
|Photocurable ink composition and inkjet recording method
|Mar 29, 2006
|Dec 24, 2009
|Keitaro Nakano
|Ink Composition
|Jul 9, 2007
|Sep 23, 2010
|Katia Studer
|Method of bonding
|Sep 30, 2010
|Jan 20, 2011
|Seiko Epson Corporation
|Inkjet-recording non-aqueous ink composition, inkjet recording method, and recorded matter
|May 27, 2009
|Jun 9, 2011
|Basf Se
|Photoinitiator mixtures
|Jan 28, 2011
|Jul 28, 2011
|Seiko Epson Corporation
|Aqueous ink composition, ink jet recording method and recorded material
|Jan 28, 2011
|Jul 28, 2011
|Seiko Epson Corporation
|Aqueous ink composition, ink jet recording method, and recorded matter
|Oct 17, 2003
|Nov 5, 2008
|Improvement in the storage stability of photoinitiators
|Nov 29, 2010
|Apr 20, 2011
|Composite multi-functional-group photoinitiator
|Jun 28, 2010
|May 23, 2012
|Michael addition reaction product and active energy ray-curable composition
|Jun 28, 2010
|Jul 22, 2015
|Michael addition reaction product and active energy ray-curable composition
|Sep 3, 2014
|Mar 9, 2016
|Alpha-amino acetophenone photoinitiator preparation method
|Dec 3, 1997
|May 15, 2008
|Ciba Specialty Chemicals Holding Inc.
|α-Aminoacetophenonverbindungen, Massen, die diese Verbindungen enthalten und deren Verwendung als Photostarter
|Jun 28, 2010
|May 9, 2012
|DIC Corporation
|Michael addition reaction product and active energy ray-curable composition
|Jun 28, 2010
|Dec 5, 2012
|Dainippon Ink & Chemicals
|Michael addition reaction product and active energy ray-curable composition
|Jan 24, 2005
|Nov 20, 2013
|Ciba Holding Inc.
|Functionalised photoinitiators
|Jul 18, 2002
|Feb 6, 2003
|Ciba Specialty Chemicals Holding Inc.
|Photosensitive resin composition
|Oct 17, 2003
|May 6, 2004
|Ciba Specialty Chemicals Holding Inc.
|Improvement in the storage stability of photoinitiators
|May 27, 2009
|Dec 10, 2009
|Basf Se
|Photoinitiator mixtures
|Aug 13, 2015
|Mar 10, 2016
|Basf Se
|Polycyclic photoinitiators
|U.S. Classification
|544/87, 544/163, 544/171, 558/405, 522/109, 544/175, 522/81, 522/121, 544/121, 522/36, 522/39, 522/107, 564/342, 522/96, 544/137, 522/34, 560/38, 544/130, 544/141
|International Classification
|Cooperative Classification
|European Classification
|Sep 16, 1991
Owner name: CIBA-GEIGY AG, A COMPANY OF THE SWISS CONFIDERATIO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:DESOBRY VINCENT;DIETLIKER KURT;HUSLER RINALDO;AND OTHERS;REEL/FRAME:005829/0721;SIGNING DATES FROM 19880309 TO 19880321
Owner name: CIBA-GEIGY CORPORATION, A NY CORP., NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CIBA-GEIGY AG, A COMPANY OF THE SWISS CONFIDERATION OF SWITZERLAND;REEL/FRAME:005829/0723
Effective date: 19910813
|Jun 2, 1995
|Fee payment
Year of fee payment: 4
|Oct 1, 1996
|Certificate of correction
|Mar 17, 1997
Owner name: CIBA SPECIALTY CHEMICALS CORPORATION, NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CIBA-GEIGY CORPORATION;REEL/FRAME:008519/0545
Effective date: 19961227
|May 24, 1999
|Fee payment
Year of fee payment: 8
|May 30, 2003
|Fee payment
Year of fee payment: 12